U.S. patent number 7,294,211 [Application Number 10/038,274] was granted by the patent office on 2007-11-13 for non-toxic corrosion-protection conversion coats based on cobalt.
This patent grant is currently assigned to University of Dayton. Invention is credited to Andrew Wells Phelps, Jeffrey Allen Sturgill, Joseph Thomas Swartzbaugh.
United States Patent |
7,294,211 |
Sturgill , et al. |
November 13, 2007 |
Non-toxic corrosion-protection conversion coats based on cobalt
Abstract
Conversion coatings based on cobalt are described for substrate
metals such as aluminum, zinc, magnesium, titanium, cadmium,
silver, copper, tin, lead, cobalt, zirconium, beryllium, or indium,
their alloys, or items coated with these metals. The conversion
coating contains a trivalent or tetravalent cobalt/valence
stabilizer complex. The coating bath may also contain a preparative
agent or solubility control agent. The oxidized cobalt is present
in the coating in a "sparingly soluble" form. The valence
stabilizers can be either inorganic or organic in nature.
Cobalt/valence stabilizer combinations are chosen based on the
well-founded principles of cobalt coordination chemistry. A number
of cobalt/valence stabilizer combinations that match the
performance of conventional hexavalent chromium systems are
presented.
Inventors: |
Sturgill; Jeffrey Allen
(Fairborn, OH), Phelps; Andrew Wells (Kettering, OH),
Swartzbaugh; Joseph Thomas (Phillipsburg, OH) |
Assignee: |
University of Dayton (Dayton,
OH)
|
Family
ID: |
21899006 |
Appl.
No.: |
10/038,274 |
Filed: |
January 4, 2002 |
Prior Publication Data
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Document
Identifier |
Publication Date |
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US 20030234063 A1 |
Dec 25, 2003 |
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Current U.S.
Class: |
148/273;
106/14.05; 106/14.21; 148/243; 252/387; 252/389.1 |
Current CPC
Class: |
C23C
22/34 (20130101); C23C 22/56 (20130101); C23C
22/68 (20130101); Y10T 428/31656 (20150401); Y10T
428/31678 (20150401) |
Current International
Class: |
C23C
22/48 (20060101) |
Field of
Search: |
;148/243,273
;106/14.05,14.21 ;252/387,389.1 |
References Cited
[Referenced By]
U.S. Patent Documents
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Other References
Chemical Abstract Registry citation 100687-47-6, Mar. 1986. cited
by other .
Chemical Abstract Registry citation 256459-53-7, Feb. 2000. cited
by other.
|
Primary Examiner: Sheehan; John P.
Attorney, Agent or Firm: Dinsmore & Shohl LLP
Claims
What is claimed is:
1. A solid corrosion-inhibiting conversion coating formed on a
substrate metal, the conversion coating comprising cobalt, wherein
the cobalt is trivalent cobalt, or tetravalent cobalt, or
combinations thereof, and a valence stabilizer combined to form a
cobalt/valence stabilizer complex within the solid
corrosion-inhibiting conversion coating, and wherein the
cobalt/valence stabilizer complex has a solubility in water of
between about 5.times.10.sup.-1 and about 1.times.10.sup.-5 moles
per liter of cobalt at about 25.degree. C. and about 760 Torr, and
wherein the valence stabilizer is selected from an organic valence
stabilizer and an inorganic valence stabilizer, with the proviso
that the inorganic valence stabilizer is not a vanadate or a
tungstate, and the organic valence stabilizer is not a
carboxylate.
2. The conversion coating of claim 1 wherein the solubility of the
cobalt/valence stabilizer complex in water is between about
5.times.10.sup.-2 and about 5.times.10.sup.-5 moles per liter of
cobalt at about 25.degree. C. and about 760 Torr.
3. The conversion coating of claim 1 wherein there is an
electrostatic barrier layer around the cobalt/valence stabilizer
complex in aqueous solution.
4. The conversion coating of claim 1 wherein the cobalt/valence
stabilizer complex acts as an ion exchange agent towards corrosive
ions.
5. The conversion coating of claim 1 wherein the conversion coating
is between about 25 and about 10,000 nanometers thick.
6. The conversion coating of claim 5 wherein the conversion coating
is between about 100 and about 500 nanometers thick.
7. The conversion coating of claim 1 wherein the conversion coating
has a morphology which enhances adhesion of a coating applied over
the conversion coating.
8. The conversion coating of claim 1 wherein the valence stabilizer
is the inorganic valence stabilizer selected from molybdates,
niobates, tantalates, tellurates, periodates, iodates, carbonates,
antimonates, stannates, titanates, zirconates, hafnates,
bismuthates, germanates, arsenates, phosphates, borates,
aluminates, and silicates, and combinations thereof.
9. The conversion coating of claim 8 wherein the valence stabilizer
is the inorganic valence stabilizer selected from molybdates,
niobates, tantalates, tellurates, periodates, iodates, carbonates,
antimonates, and stannates, and combinations thereof.
10. The conversion coating of claim 8 wherein the cobalt/valence
stabilizer complex has a central cavity containing a cobalt ion and
an additional ion.
11. The conversion coating of claim 10 wherein the additional ion
is B.sup.+3, Al.sup.+3, Si.sup.+4, P.sup.+5, Ti.sup.+4, V.sup.+5,
V.sup.+4, Cr.sup.+6, Cr.sup.+3, Mn.sup.+4, Mn.sup.+3, Mn.sup.+2,
Fe.sup.+3, Fe.sup.+2, Co.sup.+2, Ni.sup.+2, Ni.sup.+3, Ni.sup.+4,
Cu.sup.+2, Ga.sup.+3, Ge.sup.+4, As.sup.+5, As.sup.+3, Zr.sup.+4,
or Ce.sup.+4.
12. The conversion coating of claim 1 wherein the valence
stabilizer is the organic valence stabilizer selected from
monoamines; diamines; triamines; tetraamines; pentamines;
hexamines; five- or six-membered heterocyclic rings containing one
to four nitrogen atoms optionally having additional nitrogen,
sulfur, or oxygen binding sites; five- or six-membered heterocyclic
rings containing one or two sulfur atoms and having additional
nitrogen binding sites; five- or six-membered heterocyclic rings
containing one or two oxygen atoms and having additional nitrogen
binding sites; (two-, three-, four-, six-, eight-, or ten-)membered
nitrogen, nitrogen-sulfur, or nitrogen-oxygen macrocyclics;
macrocyclic oligothioketones or dithiolenes; diazenes; thio-,
amido-, or imido-derivatives of hypophosphoric, phosphoric, or
diphosphoric acids and salts; azo compounds, triazenes, formazans,
azines, hydrazones, or Schiff Bases containing at least two azo,
imine, or azine groups; azo compounds, triazenes, formazans,
azines, hydrazones, or Schiff Bases with ortho-(for aryl) or alpha-
or beta-(for alkyl) substitution; oximes; amidines and imido
compounds; dithio ligands; amides; N-(thio)acyl
7-aminobenzylidenimines; (thio) semicarbazones; (thio)acyl
hydrazones; (thio)carbazones; silylaminoalcohols; thioalkyl amines
and imines; hydroxyalkyl imines; (thio)aryl amines and imines;
guanylureas; guanidinoureas; 2-nitrosophenols; 2-nitrophenols;
N-nitrosohydroxylamines; 1,3-monothioketones; monothiomalonamides;
2-thioacylacetamides; 2-acylthioacetamides; monothioethers;
dithioethers; trithioethers; tetrathioethers; pentathioethers;
hexathioethers; disulfides; monophosphines; diphosphines;
triphosphines; tetraphosphines; pentaphosphines; hexaphosphines;
five- or six-membered heterocyclic rings containing one or two
sulfur atoms optionally having additional sulfur, oxygen, or
phosphorus binding sites; five- or six-membered heterocyclic rings
containing one to three phosphorus atoms optionally having
additional phosphorus, nitrogen, oxygen, or sulfur binding sites;
five- or six-membered heterocyclic rings containing one to four
nitrogen atoms and having additional phosphorus binding sites;
five- or six-membered heterocyclic rings containing one or two
oxygen atoms and having additional sulfur or phosphorus binding
sites; (five-, seven-, or nine-)membered nitrogen, nitrogen-sulfur,
or nitrogen-oxygen macrocyclics; (two- to ten-)membered sulfur,
sulfur-oxygen, or sulfur-phosphorus macrocyclics, not including
oligothioketones or dithiolenes; (two- to ten-) membered
phosphorus, nitrogen-phosphorus, or oxygen-phosphorus macrocyclics;
thio-, amido-, or imido-derivative of phosphonic and diphosphonic
acids and salts; thio-, amido-, or imido-derivatives of phosphonic
and diphosphonic acids and salts containing no sulfur binding
sites; amido-, or imido-derivatives of hypophosphoric, phosphoric,
or diphosphoric acids and salts containing no sulfur binding sites;
dithioperoxydiphosphoramides; dithioperoxydiphosphoric acids and
salts; monothioperoxydiphosphoramides; monothioperoxydiphosphoric
acids and salts; monothiophosphoric acids;azo compounds, triazenes,
formazans, azines, or Schiff Bases; silylamines; silazanes;
guanidines and diguanidines; pyridinaldimines; hydrazones;
hydramides; nitriles; thioureas and thioamides; ureas and biurets;
monothio ligands; diketone ligands; dithioacyl disulfides;
1,2-dithiolates; rhodanines; dithiocarbimates; (thio)xanthates;
phosphinodithioformates; (thio)borates and (thio)boronates;
(thio)arsonic acids and salts; (thio)antimonic acids and salts;
phosphine and arsine sulfides or oxides; beta-hydroxyketones and
aldehydes; carbazates; imidosulfurous diamides; sulfurdiimines;
thiocarbonyl and mercapto oximes; 2-nitrothiophenols;
2-nitrilo(thio)phenols; acylcyanamides; beta-ketoamines;
3-aminoacrylamides and 3,3-diaminoacrylamides; 2-nitroanilines;
amine and diazine N-oxides; hydrazides and semicarbazides; (amino-
or imino-)aryl phosphines; (thio- or hydroxy-)aryl phosphines;
arsines; five- or six-membered heterocyclic rings containing one
arsenic atom optionally having additional arsenic binding sites;
(two- to six-)membered arsenic macrocyclics; selenoethers; five- or
six-membered heterocyclic rings containing one or two selenium
atoms optionally having additional selenium binding sites; (two- to
six-)membered selenium macrocyclics; 1,3-diselenoketones;
1,1-diselenolates; selenophosphoric acids and salts; cyanide,
isocyanide, and cyanamide ligands; nitrosyl and nitrite ligands;
azide ligands; thiolates and selenolates; (thio)cyanate ligands;
diene or bicyclic or tricyclic hydrocarbon ligands; and carbonyl,
halogen, or hydroxo ligands; and combinations thereof.
13. The conversion coating of claim 12 wherein the organic valence
stabilizer is selected from monoamines; diamines; triamines;
tetraamines; pentamines; hexamines; five- or six-membered
heterocyclic rings containing one to four nitrogen atoms optionally
having additional nitrogen, sulfur, or oxygen binding sites; five-
or six-membered heterocyclic rings containing one or two sulfur
atoms and having additional nitrogen binding sites; five- or
six-membered heterocyclic rings containing one or two oxygen atoms
and having additional nitrogen binding sites; (two-, three-, four-,
six-, eight-, or ten-)membered nitrogen, nitrogen-sulfur, or
nitrogen-oxygen macrocyclics; macrocyclic oligothioketones or
dithiolenes; diazenes; thio-, amido-, or imido-derivatives of
hypophosphoric, phosphoric, or diphosphoric acids and salts; azo
compounds, triazenes, formazans, azines, hydrazones, or Schiff
Bases containing at least two azo, imine, or azine groups; azo
compounds, triazenes, formazans, azines, hydrazones, or Schiff
Bases with ortho-(for aryl) or alpha- or beta-(for alkyl)
substitution; oximes; amidines and imido compounds; dithio ligands;
amides; N-(thio)acyl 7-aminobenzylidenimines; (thio)
semicarbazones; (thio)acyl hydrazones; (thio)carbazones;
silylaminoalcohols; thioalkyl amines and imines; hydroxyalkyl
imines; (thio)aryl amines and imines; guanylureas; guanidinoureas;
2-nitrosophenols; 2-nitrophenols; N-nitrosohydroxylamines;
1,3-monothioketones; monothiomalonamides; 2-thioacylacetamides;
2-acylthioacetamides; dithiodicarbonic diamides; and and
combinations thereof.
14. The conversion coating of claim 12 wherein the organic valence
stabilizer is the diazene selected from diazeneformimidamides;
diazeneformamides; diazeneformothioamides; diazeneacetimidamides;
diazeneacetothioamides; diazeneformimidic acids and salts;
diazeneacetimidic acids and salts; diazeneformaldehydes;
diazeneformothioaldehydes; diazeneacetaldehydes;
diazeneacetothioaldehydes; diazenediformamides;
diazenediformothioamides; diazenediacetamides;
diazenediacetothioamides; imidoyldiazenes; diazenediformimidamides;
diazenediacetimidamides; diazenediformimidic acids and salts;
diazenediacetimidic acids and salts; diazenediformaldehydes;
diazenediformothioaldehydes; diazenediacetaldehydes;
diazenediacetothioaldehydes; and diimidoyldiazenes; and
combinations thereof.
15. The conversion coating of claim 12 wherein the organic valence
stabilizer is the thio-, amido-, or imido-derivative of
hypophosphoric, phosphoric, or diphosphoric acids and salts
selected from phosphoramidimidic triamides; phosphoramidimidic
acids and salts; phosphorodiamidimidic acids and salts; (di- or
mono-)thiohypophosphoric acids and salts; (di- or
mono-)thiohypophosphoramides; phosphoramidic acids and salts;
phosphorimidic acids and salts; (di- or mono-)thioimidodiphosphoric
acids and salts; (di- or mono-) thiohydrazidodiphosphoric acids and
salts; (di- or mono-)thioimidodiphosphoramides; (di- or
mono-)thiohydrazidodiphosphoramides; phosphoric triamides; (di- or
mono-) thiodiphosphoramides; (di- or mono-)thiodiphosphoric acids
and salts; (tetra-, tri-, di-) thiophosphoric acids and salts; and
combinations thereof.
16. The conversion coating of claim 12 wherein the organic valence
stabilizer is azo compounds, triazenes, formazans, azines,
hydrazones, or Schiff Bases with ortho-(for aryl) or alpha- or
beta-(for alkyl) substitution wherein the substituent is selected
from amino; imino; oximo; diazeno; hydrazido; thiol; mercapto;
thiocarbonyl; hydroxy; and carbonyl substituents; and combinations
thereof.
17. The conversion coating of claim 12 wherein the organic valence
stabilizer is the oxime selected from monooximes; dioximes;
carbonyl oximes; imine oximes; hydroxy oximes; amino oximes; amido
oximes; hydrazone oximes; and azo oximes; and combinations
thereof.
18. The conversion coating of claim 12 wherein the organic valence
stabilizer is the amidine and imido compound selected from
amidines; diamidines; biguanides; biguanidines; diamidinomethanes;
imidoylguanidines; amidinoguanidines; diformamidine oxides,
sulfides, and disulfides; imidodicarbonimidic acids and salts;
diimidodicarbonimidic acids and salts; thioimidodicarbonimidic
acids and salts; thiodiimidodicarbonimidic acids and salts;
diimidoylimines; diimidoylhydrazides; imidosulfamides;
diimidosulfamides; N-hydroxy(or N,N'-dihydroxy)amidines; and
diimidosulfuric acids and salts; and combinations thereof.
19. The conversion coating of claim 12 wherein the organic valence
stabilizer is the dithio ligand selected from
dithioimidodialdehydes; dithiohydrazidodialdehydes;
1,3-dithioketones; 1,2-dithioketones; dithiomalonamides;
2-thioacylthioacetamides; dithioacyl sulfides;
beta-mercaptothioketones and aldehydes;
N-(aminomethylthiol)thioureas; dithiooxamides; 1,1-dithiolates ;and
dithiocarbazates; and combinations thereof.
20. The conversion coating of claim 12 wherein the organic valence
stabilizer is the amide selected from monoamides; lactams;
amidinoamides; guanidinoamides; imidoylamides; polyamides; and
polylactams; and combinations thereof.
21. The conversion coating of claim 12 wherein the organic valence
stabilizer is the thio-, amido-, or imido-derivative of phosphonic
and diphosphonic acids and salts selected from phosphonitrile
amides; phosphonimidic diamides; phosphonamidimidic acids and
salts; dithioimidodiphosphonic acids and salts;
dithiohydrazidodiphosphonic acids and salts;
dithioimidodiphosphonamides; dithiohydrazidodiphosphonamides;
dithiodiphosphonamides; dithiodiphosphonic acids and salts;
dithioperoxydiphosphonamides; dithioperoxydiphosphonic acids and
salts; (di- and tri-) thiophosphonic acids and salts;
monothioimidodiphosphonic acids and salts;
monothiohydrazidodiphosphonic acids and salts;
monothioimidodiphosphonamides; monothiohydrazidodiphosphonamides;
monothiodiphosphonamides; monothiodiphosphonic acids and salts;
monothioperoxydiphosphonamides; monothioperoxydiphosphonic acids
and salts; monothiophosphonic acids and salts; and combinations
thereof.
22. The conversion coating of claim 12 wherein the organic valence
stabilizer is the amido-, or imido-derivative of hypophosphoric,
phosphoric, or diphosphoric acids and salts containing no sulfur
binding sites selected from hypophosphoric acids and salts;
hypophosphoramides; imidodiphosphoric acids and salts;
hydrazidodiphosphoric acids and salts; imidodiphosphoramides;
hydrazidodiphosphoramides; and diphosphoramides; and combinations
thereof.
23. The conversion coating of claim 12 wherein the organic valence
stabilizer is the amido-, or imido-derivative of phosphonic or
diphosphonic acids and salts containing no sulfur binding sites
selected from imidodiphosphonic acids and salts;
hydrazidodiphosphonic acids and salts; imidodiphosphonamides;
hydrazidodiphosphonamides; diphosphonamides; phosphonimidic acids
and salts; phosphonamidic acids and salts; and phosphonic diamides;
and combinations thereof.
24. The conversion coating of claim 12 wherein the organic valence
stabilizer is the thiourea and thioamide selected from thioureas;
thiocarboxamides; thioacylthioureas, acylthioureas, and
thioacylureas; thioaroylthioureas, aroylthioureas, and
thioaroylureas; thioimidates; thioguanylureas; guanidinothioureas;
amidinothioamides; guanidinothioamides; imidoylthioamides;
3-aminothioacrylamides; thiohydrazides; thiosemicarbazides; (mono-
and di-) thiobiurets; (mono- and di-)thioisobiurets; (mono- and
di-)thiobiureas; N-(aminomethylol) thioureas;
N-(aminomethylthiol)ureas; and beta-mercaptocarboxamides; and
combinations thereof.
25. The conversion coating of claim 12 wherein the organic valence
stabilizer is the urea and biuret selected from ureas; pseudoureas;
biurets; isobiurets; biureas; acylureas; aroylureas; and
N-(aminomethylol)ureas; and combinations thereof.
26. The conversion coating of claim 12 wherein the organic valence
stabilizer is the monothio ligand selected from beta-aminothiones;
N-thioacyl benzylidenimines; thioimidodialdehydes;
thiohydrazidodialdehydes; 1,2-monothioketones;
trithioperoxydicarbonic diamides; dithioperoxydicarbonic diamides;
beta-hydroxythioketones; beta-hydroxythioaldehydes;
beta-mercaptoketones; beta-mercaptoaldehydes; monothiooxamides;
monothiocarbazates; monothiocarbimates; mercaptoalcohols; and
silylmercaptoalcohols; and combinations thereof.
27. The conversion coating of claim 12 wherein the organic valence
stabilizer is the diketone ligand selected from imidodialdehydes;
hydrazidodialdehydes; imidodisulfamic acids and salts;
imidodisulfuric acids and salts; 1,3-diketones; 1,2-diketones;
malonamides; 2-acylacetamides; monothiodicarbonic diamides;
oxamides; and combinations thereof.
28. The conversion coating of claim 12 wherein the organic valence
stabilizer is the phosphine and arsine sulfide or oxide selected
from phosphine P-sulfides; aminophosphine sulfides; arsine
As-sulfides; aminoarsine sulfides; phosphine P-oxides;
aminophosphine oxides; arsine As-oxides; and aminoarsine oxides;
and combinations thereof.
29. The conversion coating of claim 12 wherein the solubility in
water of the cobalt/valence stabilizer complex is adjusted by the
addition of a substituent group on the organic valence
stabilizer.
30. The conversion coating of claim 29 wherein the solubility in
water is increased by the addition of the substituent group
selected from sulfonate groups (--SO.sub.3.sup.-), hydroxyl groups
(--OH), ester groups (--C.sub.3--), carbonyl groups (.dbd.C.dbd.O),
amine groups (--NH.sub.2), nitrosamine groups (.dbd.N--N.dbd.O),
carbonylnitrene groups (--CO--N), sulfoxide groups (.dbd.S.dbd.O),
sulfone groups (.dbd.S[.dbd.O].sub.2X), sulfinyl groups
(--N.dbd.S.dbd.O), sulfodiimines (.dbd.S[NH].sub.2), sulfonyl
halide groups (--S[.dbd.O].sub.2X), sulfonamide groups
(--S[.dbd.O].sub.2NH.sub.2), monohalosulfonamide groups
(--S[.dbd.O].sub.2NHX), dihalosulfonamide groups
(--S[O].sub.2MX.sub.2), halosulfonate groups (--S[.dbd.O].sub.2OX),
halosulfonate amide groups (.dbd.N--S[.dbd.O].sub.2X),
aminosulfonate groups (.dbd.N--S[.dbd.O].sub.2OH), iminosulfonate
groups (--N[SO.sub.3.sup.-].sub.1-2), phosphonate groups
(--PO.sub.3.sup.-2), phosphonamide groups
(--PO.sub.2NH.sub.2.sup.-), phosphondiamide groups
(--PO[NH.sub.2].sub.2), aminophosphonate groups
(.dbd.N--PO.sub.3.sup.-2), and iminophosphonate groups
(--N[PO.sub.3.sup.2].sub.1-2), and combinations thereof.
31. The conversion coating of claim 29 wherein the solubility in
water is decreased by the addition of the substituent group
selected from nitro groups (--NO.sub.2), perfluoroalkyl groups
(--C.sub.xF.sub.2x+1), perchloroalkyl groups
(--C.sub.xCl.sub.2x+1), nitramine groups (.dbd.N--NO.sub.2),
thioketone groups (.dbd.C.dbd.S), sulfenyl halide groups (--S--X),
and sulfur dihaloimide groups (--N.dbd.SX.sub.2), and combinations
thereof.
32. The conversion coating of claim 12 wherein an electrostatic
barrier layer of the cobalt/valence stabilizer complex is adjusted
by the addition of a substituent group on the organic valence
stabilizer.
33. The conversion coating of claim 32 wherein the electrostatic
barrier layer is increased by the addition of the substituent group
selected from ketones (.dbd.C.dbd.O), thioketones (.dbd.C.dbd.S),
amides (--C[.dbd.O]--NR.sub.2), thioamides (--C[.dbd.S]--NR.sub.2),
nitriles or cyano groups, (--CN), isocyanides (--NC), nitroso
groups (--N.dbd.O), thionitroso groups (--N.dbd.S), nitro groups
(--NO.sub.2), azido groups (--N.sub.3), cyanamide or cyanonitrene
groups (.dbd.N--CN), cyanate groups (--O--CN), isocyanate groups
(--N.dbd.C.dbd.O), thiocyanate groups (--S--CN), isothiocyanate
groups (--N.dbd.C.dbd.S), nitrosamine groups (.dbd.N--N.dbd.O),
thionitrosamine groups (.dbd.N--N.dbd.S), nitramine groups
(.dbd.N--NO.sub.2), thionitramine groups (.dbd.N--NS.sub.2),
carbonylnitrene groups (--CO--N), thiocarbonylnitrene groups
(--CS--N), sulfenyl halides (--S--X), sulfoxides (.dbd.S.dbd.O),
sulfones (.dbd.S[.dbd.O].sub.2), sulfinyl groups (--N.dbd.S.dbd.O),
thiosulfinyl groups (--N.dbd.S.dbd.S), sulfenyl thiocyanato groups
(--S--S--CN), sulfenyl cyanato groups (--S--O--CN), sulfodiimine
groups (.dbd.S[.dbd.NH].sub.2), sulfur dihaloimido groups
(--N.dbd.SX.sub.2), sulfur oxide dihaloimido groups
(--N.dbd.S[.dbd.O]X.sub.2), aminosulfur oxide trihalide groups
(.dbd.N--S[.dbd.O]X.sub.3), sulfonyl azide groups
(--S[.dbd.O].sub.2N.sub.3), sulfonyl thiocyanate groups
(--S[.dbd.O].sub.2SCN), sulfonyl cyanate groups
(--S[.dbd.O].sub.2OCN), sulfonyl cyanide groups
(--S[.dbd.O].sub.2CN), halosulfonate groups (--S[.dbd.O].sub.2OX),
phosphonyl thiocyanate groups (--P[.dbd.O]OHSCN), phosphonyl
cyanate groups (--P[.dbd.O]OHOCN), and phosphonyl cyanide groups
(--P[.dbd.O]OHCN), and combinations thereof.
34. The conversion coating of claim 1 further comprising a
solubility control agent.
35. The conversion coating of claim 34 wherein the solubility
control agent is selected from a cationic solubility control agent
and an anionic solubility control agent.
36. The conversion coating of claim 35 wherein the solubility
control agent is the cationic solubility control agent selected
from H.sup.+, Li.sup.+, Na.sup.+, K.sup.+, Rb.sup.+, Cs.sup.+,
NH.sub.4.sup.+, Mg.sup.+2, Ca.sup.+2, Sr.sup.+2, Be.sup.+2,
Ba.sup.+, Y.sup.+3, La.sup.3, Ce.sup.+3, Ce.sup.+4, Nd.sup.+3,
Pr.sup.+3, Sc.sup.+3, Sm.sup.+3, Eu.sup.+3, Eu.sup.+2, Gd.sup.+3,
Tb.sup.+3, Dy.sup.+3, Ho.sup.+3, Er.sup.+3, Tm.sup.+3, Yb.sup.+3,
Lu.sup.+3, Ti.sup.+4, Zr.sup.+4, Ti.sup.+3, Hf.sup.4, Nb.sup.+4,
Ta.sup.+4, Nb.sup.+4, Ta.sup.+4, V.sup.+5, V.sup.+4, V.sup.+3,
Mo.sup.+6, W.sup.+6, Mo.sup.+5, W.sup.+5, Mo.sup.+4, W.sup.+4,
Cr.sup.+3, Mn.sup.+2, Mn.sup.+3, Mn.sup.+4, Fe.sup.+2, Fe.sup.+3,
Co.sup.+2, Co.sup.+3, Ni.sup.+2, Ni.sup.+3, Ni.sup.+4, Ru.sup.+2,
Ru.sup.+3, Ru.sup.+4, Rh.sup.+3, Ir.sup.+3, Rh.sup.+2, Ir.sup.+2,
Pd.sup.+4, Pt.sup.+4, Pd.sup.+2, Pt.sup.+2, Os.sup.+4, Cu.sup.+,
Cu.sup.+2, Cu.sup.+3, Ag.sup.+, Ag.sup.+2, Ag.sup.+3, Au.sup.+,
Au.sup.+2, Au.sup.3, Zn.sup.+2, Cd.sup.+2, Hg.sup.+, Hg.sup.+2,
Al.sup.+3, Ga.sup.+3, Ga.sup.+, In.sup.+3, In.sup.+, Tl.sup.+3,
Tl.sup.+, Ge.sup.+4, Ge.sup.+2, Sn.sup.+4, Sn.sup.+2, Pb.sup.+4,
Pb.sup.+2, Sb.sup.+3, Sb.sup.+5, As.sup.+3, As.sup.+5, Bi.sup.+3,
Bi.sup.+5, organic compounds containing at least one N.sup.+ site,
organic compounds containing at least one phosphonium site, organic
compounds containing at least one arsonium site, organic compounds
containing at least one stibonium site, organic compounds
containing at least one oxonium site, organic compounds containing
at least one sulfonium site, organic compounds containing at least
one selenonium site, organic compounds containing at least one
iodonium site, and quaternary ammonium compounds having a formula
NR.sub.4.sup.+, where R is an alkyl, aromatic, or acyclic organic
constituent, and combinations thereof.
37. The conversion coating of claim 36 wherein the cationic
solubility control agent is selected from H.sup.+, Li.sup.+,
Na.sup.+, K.sup.+, Rb.sup.+, Cs.sup.+, NH.sub.4.sup.+, Mg.sup.+2,
Ca.sup.+2, Sr.sup.+2, Y.sup.+3, La.sup.+3, Ce.sup.+3, Ce.sup.+4,
Nd.sup.+3, Pr.sup.+, Sc.sup.+3, Sm.sup.+3, Eu.sup.+3, Eu.sup.+2,
Gd.sup.+3, Tb.sup.+3, Dy.sup.+3, Ho.sup.+3, Er.sup.+3, Tm.sup.+3,
Yb.sup.+3, Lu.sup.+3, Ti.sup.+4, Zr.sup.+4, Ti.sup.+3, Hf.sup.+4,
Nb.sup.+5, Ta.sup.+5, Nb.sup.+4, Ta.sup.+4, Mo.sup.+6, W.sup.+6,
Mo.sup.+5, W.sup.+5, Mo.sup.+4, W.sup.+4, Mn.sup.+2, Mn.sup.+3,
Mn.sup.+4, Fe.sup.2, Fe.sup.+3, Co.sup.+2, Co.sup.+3, Ru.sup.+2,
Ru.sup.+3, Ru.sup.+4, Rh.sup.+3, Ir.sup.+3, Rh.sup.+2, Ir.sup.+2,
Pd.sup.+4, Pt.sup.+4, Pd.sup.+2, Pt.sup.+2, Cu.sup.+, Cu.sup.+2,
Cu.sup.+3, Ag.sup.+, Ag.sup.+2, Ag.sup.+3, Au.sup.+, Au.sup.+2,
Au.sup.+3, Zn.sup.+2, Al.sup.+3, Ga.sup.+3, Ga.sup.+, In.sup.+3,
In.sup.+, Ge.sup.+4, Ge.sup.+2, Sn.sup.+4, Sn.sup.+2, Sb.sup.+3,
Sb.sup.+5, Bi.sup.+3, Bi.sup.+5, organic compounds containing at
least one N.sup.+ site, organic compounds containing at least one
phosphonium site, organic compounds containing at least one
stibonium site, organic compounds containing at least one oxonium
site, organic compounds containing at least one sulfonium site,
organic compounds containing at least one iodonium site, and
quaternary ammonium compounds having a formula NR.sub.4.sup.+,
where R is an alkyl, aromatic, or acyclic organic constituent, and
combinations thereof.
38. The conversion coating of claim 35 wherein the solubility
control agent is the anionic solubility control agent selected from
fluorotitanates; chlorotitanates; fluorozirconates;
chlorozirconates; fluoroniobates; chloroniobates; fluorotantalates;
chlorotantalates; molybdates; tungstates; permanganates;
fluoromanganates; chloromanganates; fluoroferrates; chloroferrates;
fluorocobaltates; chlorocobaltates; fluorozincates; chlorozincates;
borates; fluoroborates; fluoroaluminates; chloroaluminates;
carbonates; silicates; fluorosilicates; fluorostannates; nitrates;
nitrites; azides; cyanamides; phosphates; phosphites; phosphonates;
phosphinites; thiophosphates; thiophosphites; thiophosphonates;
thiophosphinites; fluorophosphates; fluoroantimonates;
chloroantimonates; sulfates; sulfites; sulfonates; thiosulfates;
dithionites; dithionates; fluorosulfates; tellurates; fluorides;
chlorides; chlorates; perchlorates; bromides; bromates; iodides;
iodates; periodates; heteropolyanions; ferricyanides;
ferrocyanides; cyanocobaltates; cyanocuprates; cyanomanganates;
cyanates; cyanatofenates; cyanatocobaltates; cyanatocuprates;
cyanatomanganates; thiocyanates; thiocyanatoferrates;
thiocyanatocobaltates; thiocyanatocuprates; thiocyanatomanganates;
cyanamides; cyanamidoferrates; cyanamidocobaltates;
cyanamidocuprates; cyanamidomanganates; nitritofenates;
nitritocobaltates; azides; (thio)carboxylates;
di(thio)carboxylates; tri(thio)carboxylates;
tetra(thio)carboxylates; (thio)phenolates; di(thio)phenolates;
tri(thio)phenolates; tetra(thio)phenolates; (thio)phosphonates;
di(thio)phosphonates; tri(thio)phosphonates; (thio)phosphonamides;
di(thio)phosphonamides; tri(thio)phosphonamides;
amino(thio)phosphonates; diamino(thio)phosphonates;
triamino(thio)phosphonates; imino(thio)phosphonates;
diimino(thio)phosphonates; (thio)sulfonates; di(thio)sulfonates;
tri(thio)sulfonates; (thio) sulfonamides; di(thio) sulfonamides;
tri(thio)sulfonamides; amino(thio) sulfonates; diamino(thio)
sulfonates; triamino(thio)sulfonates; imino(thio)sulfonates;
diimino(thio) sulfonates; (thio)borates; di(thio)borates;
(thio)boronates; organic silicates; stibonates; cyanides;
cyanochromates; cyanonickelates; cyanatochromates;
cyanatonickelates; thiocyanatochromates; thiocyanatonickelates;
cyanamidochromates; cyanamidonickelates; nitritonickelates;
arsonates; diarsonates; triarsonates; organic selenates;
diselenates; triselenates; arsenates; arsenites; fluoroarsenates;
chloroarsenates; selenates; selenites; fluorothallates;
chlorothallates; iodomercury anions; chloromercurates;
bromomercurates; osmates; fluoronickelates; chromates; Reinecke's
salt; and vanadates; and combinations thereof.
39. The conversion coating of claim 38 wherein the anionic
solubility control agent is selected from fluorotitanates;
chlorotitanates; fluorozirconates; chlorozirconates;
fluoroniobates; chloroniobates; fluorotantalates; chlorotantalates;
molybdates; tungstates; permanganates; fluoromanganates;
chloromanganates; fluoroferrates; chloroferrates; fluorocobaltates;
chlorocobaltates; fluorozincates; chlorozincates; borates;
fluoroborates; fluoroaluminates; chloroaluminates; carbonates;
silicates; fluorosilicates; fluorostannates; nitrates; nitrites;
azides; cyanamides; phosphates; phosphites; phosphonates;
phosphinites; thiophosphates; thiophosphites; thiophosphonates;
thiophosphinites; fluorophosphates; fluoroantimonates;
chloroantimonates; sulfates; sulfites; sulfonates; thiosulfates;
dithionites; dithionates; fluorosulfates; tellurates; fluorides;
chlorides; chlorates; perchlorates; bromides; bromates; iodides;
iodates; periodates; heteropolyanions; ferricyanides;
ferrocyanides; cyanocobaltates; cyanocuprates; cyanomanganates;
cyanates; cyanatofenates; cyanatocobaltates; cyanatocuprates;
cyanatomanganates; thiocyanates; thiocyanatoferrates;
thiocyanatocobaltates; thiocyanatocuprates; thiocyanatomanganates;
cyanamides; cyanamidoferrates; cyanamidocobaltates;
cyanamidocuprates; cyanamidomanganates; nitritofenates;
nitritocobaltates; azides; (thio)carboxylates;
di(thio)carboxylates; tri(thio)carboxylates;
tetra(thio)carboxylates; (thio)phenolates; di(thio)phenolates;
tri(thio)phenolates; tetra(thio)phenolates; (thio)phosphonates;
di(thio)phosphonates; tri(thio)phosphonates; (thio)phosphonamides;
di(thio)phosphonamides; tri(thio)phosphonamides;
amino(thio)phosphonates; diamino(thio)phosphonates;
triamino(thio)phosphonates; imino(thio)phosphonates;
diimino(thio)phosphonates; (thio)sulfonates; di(thio)sulfonates;
tri(thio)sulfonates; (thio)sulfonamides; di(thio)sulfonamides;
tri(thio)sulfonamides; amino(thio)sulfonates; diamino(thio)
sulfonates; triamino(thio)sulfonates; imino(thio)sulfonates;
diimino(thio)sulfonates; (thio)borates; di(thio)borates;
(thio)boronates; organic silicates; and stibonates; and
combinations thereof.
40. The conversion coating of claim 1 wherein the conversion
coating is colored.
41. The conversion coating of claim 40 further comprising an agent
which improves color-fastness of the conversion coating.
42. The conversion coating of claim 41 wherein the agent which
improves color-fastness is selected from an active UV blocker, a
passive UV blocker, and a brightener.
43. The conversion coating of claim 42 wherein the agent which
improves color-fastness is the active UV blocker selected from
carbon black, graphite, and phthalocyanines.
44. The conversion coating of claim 42 wherein the agent which
improves color-fastness is the passive UV blocker selected from
titanium oxide, tin oxide, lead oxide, silicon oxide, silicates,
and aluminosilicates, and combinations thereof.
45. The conversion coating of claim 42 wherein the agent which
improves color-fastness is the brightener selected from sulfonic
acids, sulfonates, sulfonamides, sulfonimides, sulfinic acids,
sulfones, cyanides, and nonionic surfactants.
46. A corrosion-inhibiting conversion coating bath consisting
essentially of a solvent, a precursor cobalt source, and a valence
stabilizer combined to form a cobalt/valence stabilizer complex,
optionally an oxidizer, optionally preparative agent, and
optionally a solubility control agent, and wherein the valence
stabilizer is selected from an organic valence stabilizer and an
inorganic valence stabilizer, with the proviso that the inorganic
valence stabilizer is not a vanadate or a tungstate, and the
organic valence stabilizer is not a carboxylate.
47. The conversion coating bath of claim 46 wherein the solvent is
water.
48. The conversion coating bath of claim 46 wherein the conversion
coating bath includes the oxidizer selected from a dissolved solid,
a liquid, and a gas.
49. The conversion coating bath of claim 48 wherein the oxidizer is
selected from peroxides, superoxides, persulfates, perborates,
pemitrates, perphosphates, percarbonates, persilicates,
peraluminates, pertitanates, perzirconates, permolybdates,
pertungstates, pervanadates, organic peroxyacid derivatives, ozone,
hypochlorites, chlorates, perchlorates, nitrates, nitrites,
vanadates, iodates, hypobromites, chlorites, bromates,
permanganates, periodates, dissolved oxygen, dissolved chlorine,
and dissolved fluorine, and combinations thereof.
50. The conversion coating bath of claim 46 wherein the cobalt
source is selected from cobalt contained within a treated
substrate, cobalt nitrate, cobalt sulfate, cobalt perchlorate,
cobalt chloride, cobalt fluoride, cobalt bromide, cobalt iodide,
cobalt bromate, cobalt chlorate, cobalt fluosilicate, cobalt
fluotitanate, cobalt fluozirconate, cobalt fluoborate, cobalt
fluoaluminate, cobalt formate, cobalt acetate, cobalt propionate,
cobalt butyrate, cobalt benzoate, cobalt glycolate, cobalt lactate,
cobalt tartronate, cobalt malate, cobalt tartrate, cobalt citrate,
cobalt benzenesulfonate, cobalt thiocyanate, cobalt
acetylacetonate, ammonium cobalt sulfate, ammonium cobalt nitrate,
ammonium cobalt chloride, ammonium cobalt bromide, hexaamminecobalt
chloride, hexaamminecobalt bromide, hexaamminecobalt nitrate,
pentaamminecobalt chloride, pentaamminecobalt bromide,
pentaamminecobalt nitrate, lithium cobaltinitrite, sodium
cobaltinitrite, tris(ethylenediamine)cobalt chloride,
tris(ethylenediamine)cobalt nitrate, bipyridine complexes of
trivalent cobalt, phenanthroline complexes of trivalent cobalt, and
cobalticarbonates, and combinations thereof.
51. The conversion coating bath of claim 46 wherein the conversion
coating bath includes the preparative agent selected from
fluorides, chlorides, bromides, and hydroxides, and combinations
thereof.
52. The conversion coating bath of claim 51 wherein the preparative
agent is a fluoride.
53. The conversion coating bath of claim 52 wherein the fluoride is
selected from fluorozirconates, fluorotitanates, fluorosilicates,
fluoroaluminates, fluoroborates, fluorogallates, fluoroindates,
fluorogermanates, fluorostannates, fluorophosphates,
fluoroarsenates, fluoroantimonates, fluorobismuthates,
fluorosulfates, fluoroselenates, fluorotellurates, fluorocuprates,
fluoroargentates, fluorozincates, fluorohafnates, fluorovanadates,
fluoroniobates, fluorotantalates, fluoromolybdates,
fluorotungstates, fluoroyttrates, fluorolanthanates, fluorocerates,
fluoromanganates, fluoroferrates, fluoronickelates,
fluorocobaltates, potassium fluoride, potassium hydrogen fluoride,
sodium fluoride, sodium hydrogen fluoride, lithium fluoride,
lithium hydrogen fluoride, ammonium fluoride, ammonium hydrogen
fluoride, hydrofluoric acid, dissolved fluorine, and organic
fluorides, and combinations thereof.
54. The conversion coating bath of claim 46 wherein the conversion
coating bath includes the solubility control agent selected from a
cationic solubility control agent and an anionic solubility control
agent.
55. The conversion coating bath of claim 54 wherein the solubility
control agent is the cationic solubility control agent selected
from H.sup.+, Li.sup.+, Na.sup.+, K.sup.+, Rb.sup.+, Cs.sup.+,
NH.sub.4.sup.+, Mg.sup.+2, Ca.sup.+2, Sr.sup.+2, Y.sup.+3,
La.sup.+3, Ce.sup.+3, Ce.sup.+4, Nd.sup.+3, P.sup.+3, Sc.sup.+3,
Sm.sup.+3, Eu.sup.+3, Eu.sup.+2, Gd.sup.+, Tb.sup.+3, Dy.sup.+3,
Ho.sup.+3, Er.sup.+3, Tm.sup.+3, Yb.sup.+3, Lu.sup.+3, Ti.sup.+4,
Zr.sup.+4, Ti.sup.+3, Hf.sup.4, Nb.sup.+5, Ta.sup.+5, Nb.sup.+4,
Ta.sup.+4, Mo.sup.+6, W.sup.+6, Mo.sup.+5, W.sup.+5, Mo.sup.+4,
W.sup.+4, Mn.sup.+2, Mn.sup.+3, Mn.sup.+4, Fe.sup.+2, Fe.sup.+3,
Co.sup.+2, Co.sup.+3, Ru.sup.+2, Ru.sup.+3, Ru.sup.+4, Rh.sup.+3,
Ir.sup.3, Rh.sup.+2, Ir.sup.+2, Pd.sup.+4, Pt.sup.+4, Pd.sup.+2,
Pt.sup.+2, Cu.sup.+, Cu.sup.+2, Cu.sup.+3, Ag.sup.+, Ag.sup.+2,
Ag.sup.+3, Au.sup.+, Au.sup.+2 Au.sup.+3, Zn.sup.+2, Al.sup.+3,
Ga.sup.+3, Ga.sup.+, In.sup.+3, In.sup.+, Ge.sup.+4, Ge.sup.+2,
Sn.sup.+4, Sn.sup.+2, Sb.sup.+3, Sb.sup.+5, Bi.sup.+3, Bi.sup.+5,
organic compounds containing at least one N.sup.+ site, organic
compounds containing at least one phosphonium site, organic
compounds containing at least one arsonium site, organic compounds
containing at least one stibonium site, organic compounds
containing at least one oxonium site, organic compounds containing
at least one sulfonium site, organic compounds containing at least
one selenonium site, organic compounds containing at least one
iodonium site, and quaternary ammonium compounds having a formula
NR.sub.4.sup.+, where R is an alkyl, aromatic, or acyclic organic
constituent, and combinations thereof.
56. The conversion coating bath of claim 55 wherein the cationic
solubility control agent is selected from H.sup.+, Li.sup.+,
Na.sup.+, K.sup.+, Rb.sup.+, Cs.sup.+, NH.sub.4.sup.+, Mg.sup.+2,
Ca.sup.+2, Sr.sup.+2, Y.sup.+3, La.sup.+3, Ce.sup.+3, Ce.sup.+4,
Nd.sup.+3, P.sup.+3, Sc.sup.+3, Sm.sup.+3, Eu.sup.+3, Eu.sup.+2,
Gd.sup.+, Tb.sup.+3, Dy.sup.+3, Ho.sup.+3, Er.sup.+3, Tm.sup.+3,
Yb.sup.+3, Lu.sup.+3, Ti.sup.+4, Zr.sup.+4, Ti.sup.+3, Hf.sup.4,
Nb.sup.+5, Ta.sup.+5, Nb.sup.+4, Ta.sup.+4, Mo.sup.+6, W.sup.+6,
Mo.sup.+5, W.sup.+5, Mo.sup.+4, W.sup.+4, Mn.sup.+2, Mn.sup.+3,
Mn.sup.+4, Fe.sup.+2, Fe.sup.+3, Co.sup.+2, Co.sup.+3, Ru.sup.+2,
Ru.sup.+3, Ru.sup.+4, Rh.sup.+3, Ir.sup.3, Rh.sup.+2, Ir.sup.+2,
Pd.sup.+4, Pt.sup.+4, Pd.sup.+2, Pt.sup.+2, Cu.sup.+, Cu.sup.+2,
Cu.sup.+3, Ag.sup.+, Ag.sup.+2, Ag.sup.+3, Au.sup.+, Au.sup.+2
Au.sup.+3, Zn.sup.+2, Al.sup.+3, Ga.sup.+3, Ga.sup.+, In.sup.+3,
In.sup.+, Ge.sup.+4, Ge.sup.+2, Sn.sup.+4, Sn.sup.+2, Sb.sup.+3,
Sb.sup.+5, Bi.sup.+3, Bi.sup.+5, organic compounds containing at
least one N.sup.+ site, organic compounds containing at least one
phosphonium site, organic compounds containing at least one
stibonium site, organic compounds containing at least one oxonium
site, organic compounds containing at least one sulfonium site,
organic compounds containing at least one iodonium site, and
quaternary ammonium compounds having a formula NR.sub.4.sup.+,
where R is an alkyl, aromatic, or acyclic organic constituent, and
combinations thereof.
57. The conversion coating bath of claim 54 wherein the solubility
control agent is the anionic solubility control agent selected from
fluorotitanates; chlorotitanates; fluorozirconates;
chlorozirconates; fluoroniobates; chloroniobates; fluorotantalates;
chlorotantalates; molybdates; tungstates; permanganates;
fluoromanganates; chloromanganates; fluoroferrates; chloroferrates;
fluorocobaltates; chlorocobaltates; fluorozincates; chlorozincates;
borates; fluoroborates; fluoroaluminates; chloroaluminates;
carbonates; silicates; fluorosilicates; fluorostannates; nitrates;
nitrites; azides; cyanamides; phosphates; phosphites; phosphonates;
phosphinites; thiophosphates; thiophosphites; thiophosphonates;
thiophosphinites; fluorophosphates; fluoroantimonates;
chloroantimonates; sulfates; sulfites; sulfonates; thiosulfates;
dithionites; dithionates; fluorosulfates; tellurates; fluorides;
chlorides; chlorates; perchlorates; bromides; bromates; iodides;
iodates; periodates; heteropolyanions; fenicyanides; fenocyanides;
cyanocobaltates; cyanocuprates; cyanomanganates; cyanates;
cyanatoferrates; cyanatocobaltates; cyanatocuprates;
cyanatomanganates; thiocyanates; thiocyanatoferrates;
thiocyanatocobaltates; thiocyanatocuprates; thiocyanatomanganates;
cyanamides; cyanamidofenates; cyanamidocobaltates;
cyanamidocuprates; cyanamidomanganates; nitritofenates;
nitritocobaltates; azides; (thio)carboxylates;
di(thio)carboxylates; tri(thio)carboxylates;
tetra(thio)carboxylates ; (thio)phenolates; di(thio)phenolates;
tri(thio)phenolates; tetra(thio)phenolates; (thio)phosphonates;
di(thio)phosphonates; tri(thio)phosphonates; (thio)phosphonamides;
di(thio)phosphonamides; tri(thio)phosphonamides;
amino(thio)phosphonates; diamino(thio)phosphonates;
triamino(thio)phosphonates; imino(thio)phosphonates;
diimino(thio)phosphonates; (thio)sulfonates; di(thio)sulfonates;
tri(thio)sulfonates; (thio)sulfonamides; di(thio)sulfonamides;
tri(thio)sulfonamides; amino(thio)sulfonates;
diamino(thio)sulfonates; triamino(thio)sulfonates;
imino(thio)sulfonates; diimino(thio)sulfonates; (thio)borates;
di(thio)borates; (thio)boronates; organic silicates; stibonates;
cyanides; cyanochromates; cyanonickelates; cyanatochromates;
cyanatonickelates; thiocyanatochromates; thiocyanatonickelates;
cyanamidochromates; cyanamidonickelates; nitritonickelates;
arsonates; diarsonates; triarsonates; organic selenates;
diselenates; triselenates; arsenates; arsenites; fluoroarsenates;
chioroarsenates; selenates; selenites; fluorothallates;
chiorothallates; iodomercury anions; chioromercurates;
bromomercurates; osmates; fluoronickelates; chromates; Reinecke's
salt; and vanadates; and combinations thereof.
58. The conversion coating bath of claim 57 wherein the anionic
solubility control agent is selected from fluorotitanates;
chlorotitanates; fluorozirconates; chlorozirconates;
fluoroniobates; chloroniobates; fluorotantalates; chlorotantalates;
molybdates; tungstates; permanganates; fluoromanganates;
chloromanganates; fluoroferrates; chloroferrates; fluorocobaltates;
chlorocobaltates; fluorozincates; chlorozincates; borates;
fluoroborates; fluoroaluminates; chloroaluminates; carbonates;
silicates; fluorosilicates; fluorostannates; nitrates; nitrites;
azides; cyanamides; phosphates; phosphites; phosphonates;
phosphinites; thiophosphates; thiophosphites; thiophosphonates;
thiophosphinites; fluorophosphates; fluoroantimonates;
chloroantimonates; sulfates; sulfites; sulfonates; thiosulfates;
dithionites; dithionates; fluorosulfates; tellurates; fluorides;
chlorides; chlorates; perchlorates; bromides; bromates; iodides;
iodates; periodates; heteropolyanions; ferricyanides;
ferrocyanides; cyanocobaltates; cyanocuprates; cyanomanganates;
cyanates; cyanatofenates; cyanatocobaltates; cyanatocuprates;
cyanatomanganates; thiocyanates; thiocyanatoferrates;
thiocyanatocobaltates; thiocyanatocuprates; thiocyanatomanganates;
cyanamides; cyanamidoferrates; cyanamidocobaltates;
cyanamidocuprates; cyanamidomanganates; nitritofenates;
nitritocobaltates; azides; (thio)carboxylates;
di(thio)carboxylates; tri(thio)carboxylates;
tetra(thio)carboxylates; (thio)phenolates; di(thio)phenolates;
tri(thio)phenolates; tetra(thio)phenolates; (thio)phosphonates;
di(thio)phosphonates; tri(thio)phosphonates; (thio)phosphonamides;
di(thio)phosphonamides; tri(thio)phosphonamides;
amino(thio)phosphonates; diamino(thio)phosphonates;
triamino(thio)phosphonates; imino(thio)phosphonates;
diimino(thio)phosphonates; (thio)sulfonates; di(thio)sulfonates;
tri(thio)sulfonates; (thio)sulfonamides; di(thio)sulfonamides;
tri(thio)sulfonamides; amino(thio)sulfonates;
diamino(thio)sulfonates; triamino(thio)sulfonates;
imino(thio)sulfonates; diimino(thio)sulfonates; (thio)borates;
di(thio)borates; (thio)boronates; organic silicates; and
stibonates; and combinations thereof.
59. The conversion coating bath of claim 46 wherein the conversion
coating bath has a concentration of cobalt of between about
1.times.10.sup.-4 moles/liter cobalt and a concentration which is a
maximum solubility of the cobalt source in the solvent at a
temperature of the conversion coating bath.
60. The conversion coating bath of claim 48 wherein the conversion
coating bath has a concentration of oxidizer of between a minimum
concentration wherein a majority of the cobalt is oxidized to a
trivalent or tetravalent oxidation state and a maximum solubility
of the oxidizer in the solvent at a temperature of the conversion
coating bath.
61. The conversion coating bath of claim 51 wherein the conversion
coating bath has a concentration of preparative agent between a
minimum concentration wherein there is a fluoride-to-cobalt ratio
of 0.05 and a maximum concentration which is a maximum solubility
of the preparative agent in the solvent at a temperature of the
conversion coating bath.
62. The conversion coating bath of claim 46 wherein the conversion
coating bath has a concentration of valence stabilizer between a
minimum concentration wherein there is a valence
stabilizer-to-cobalt ratio of 0.010 and a maximum concentration
which is a maximum solubility of the valence stabilizer in the
solvent at a temperature of the conversion coating bath.
63. The conversion coating bath of claim 46 wherein the conversion
coating bath has a pH of between about 0 and about 7.
64. The conversion coating bath of claim 63 wherein the conversion
coating bath has a pH of between about 1 and about 6.
65. The conversion coating bath of claim 46 wherein the conversion
coating bath has a temperature of between about 50.degree. C. and
about 100.degree. C.
66. The conversion coating bath of claim 65 wherein the conversion
coating bath has a temperature of between about 50.degree. C. and
about 400.degree. C.
67. A solid conosion-inhibiting conversion coating formed on a
substrate metal, the conversion coating comprising cobalt, wherein
the cobalt is trivalent cobalt, or tetravalent cobalt, or
combinations thereof, and a valence stabilizer combined to form a
cobalt/valence stabilizer complex within the solid,
conosion-inhibiting conversion coating, wherein the cobalt/valence
stabilizer complex is sparingly soluble in water at about
25.degree. C. and about 760 Torr, and wherein the valence
stabilizer is selected from an organic valence stabilizer and an
inorganic valence stabilizer, with the proviso that the inorganic
valence stabilizer is not a vanadate or a tungstate, and the
organic valence stabilizer is not a carboxylate.
68. A conosion-inhibiting conversion coating bath comprising a
solvent, a precursor cobalt source, and a valence stabilizer
combined to form a cobalt/valence stabilizer complex, optionally an
oxidizer, optionally preparative agent, and optionally a solubility
control agent, wherein the cobalt/valence stabilizer complex is
sparingly soluble in water at about 25.degree. C. and about 760
Torr, and wherein the valence stabilizer is selected from an
organic valence stabilizer and an inorganic valence stabilizer,
with the proviso that the inorganic valence stabilizer is not a
vanadate or a tungstate, and the organic valance stabilizer is not
a carboxylate.
69. A conosion-inhibiting conversion coating comprising cobalt,
wherein the cobalt is trivalent cobalt, or tetravalent cobalt, or
combinations thereof, and a valence stabilizer combined to form a
cobalt/valence stabilizer complex wherein the cobalt/valence
stabilizer complex has a central cavity containing a cobalt ion and
an additional ion wherein the additional ion is B.sup.+3,
Al.sup.+3, Si.sup.+4, P.sup.+5, Ti.sup.+4, V.sup.+5, V.sup.+4,
Cr.sup.+6, Cr.sup.+3, Mn.sup.+4, Mn.sup.+3, Mn.sup.+2, Fe.sup.+3,
Fe.sup.+2, Co.sup.+2, Ni.sup.+2, Ni.sup.+3, Ni.sup.+4, Cu.sup.+2,
Cu.sup.+3, Zn.sup.+2, Ga.sup.+3, Ge.sup.+4, As.sup.+5, As.sup.+3,
Zr.sup.+4, or Ce.sup.+4.
70. A conosion-inhibiting conversion coating comprising cobalt,
wherein the cobalt is trivalent cobalt, or tetravalent cobalt, or
combinations thereof, and a valence stabilizer combined to form a
cobalt/valence stabilizer complex wherein the valence stabilizer is
an organic valence stabilizer selected from monoamines; diamines;
triamines; tetraamines; pentamines; hexamines; five- or
six-membered heterocyclic rings containing one to four nitrogen
atoms optionally having additional nitrogen, sulfur, or oxygen
binding sites; five- or six-membered heterocyclic rings containing
one or two sulfur atoms and having additional nitrogen binding
sites; five- or six-membered heterocyclic rings containing one or
two oxygen atoms and having additional nitrogen binding sites;
(two-, three-, four-, six-, eight-, or ten-)membered nitrogen,
nitrogen-sulfur, or nitrogen-oxygen macrocyclics; macrocyclic
oligothioketones or dithiolenes; diazenes; thio-, amido-, or
imido-derivatives of hypophosphoric, phosphoric, or diphosphoric
acids and salts; azo compounds, triazenes, formazans, azines,
hydrazones, or Schiff Bases containing at least two azo, imine, or
azine groups; azo compounds, triazenes, formazans, azines,
hydrazones, or Schiff Bases with ortho-(for aryl) or alpha- or
beta-(for alkyl) substitution; oximes; amidines and imido
compounds; dithio ligands; amides; amino acids; N-(thio)acyl
7-aminobenzylidenimines; (thio)hydroxamates; alpha- or
ortho-aminothio(di)carboxylic acids and salts;
(thio)semicarbazones; (thio)acyl hydrazones; (thio)carbazones;
silylaminoalcohols; thioalkyl amines and imines; hydroxyalkyl
imines; (thio)aryl amines and imines; guanylureas; guanidinoureas;
2-nitrosophenols; 2-nitrophenols; N-nitrosohydroxylamines;
1,3-monothioketones; monothiomalonamides; 2-thioacylacetamides;
2-acylthioacetamides; dithiodicarbonic diamides;
trithiodicarboxylic acids and salts; monothiocarbamates;
monothioethers; dithioethers; trithioethers; tetrathioethers;
pentathioethers; hexathioethers; disulfides; monophosphines;
diphosphines; triphosphines; tetraphosphines; pentaphosphines;
hexaphosphines; five- or six-membered heterocyclic rings containing
one or two sulfur atoms optionally having additional sulfur,
oxygen, or phosphorus binding sites; five- or six-membered
heterocyclic rings containing one to three phosphorus atoms
optionally having additional phosphorus, nitrogen, oxygen, or
sulfur binding sites; five- or six-membered heterocyclic rings
containing one to four nitrogen atoms and having additional
phosphorus binding sites; five- or six-membered heterocyclic rings
containing one or two oxygen atoms and having additional sulfur or
phosphorus binding sites; (five-, seven-, or nine-)membered
nitrogen, nitrogen-sulfur, or nitrogen-oxygen macrocyclics; (two-
to ten-)membered sulfur, sulfur-oxygen, or sulfur-phosphorus
macrocyclics, not including oligothioketones or dithiolenes; (two-
to ten-) membered phosphorus, nitrogen-phosphorus, or
oxygen-phosphorus macrocyclics; thio-, amido-, or imido-derivatives
of phosphonic and diphosphonic acids and salts containing no sulfur
binding sites; amido-, or imido-derivatives of hypophosphoric,
phosphoric, or diphosphoric acids and salts containing no sulfur
binding sites; dithioperoxydiphosphoramides;
dithioperoxydiphosphoric acids and salts;
monothioperoxydiphosphoramides; monothioperoxydiphosphoric acids
and salts; monothiophosphoric acids; phosphoro(dithioperoxoic)
acids and salts; azo compounds, triazenes, formazans, azines, or
Schiff Bases; silylamines; silazanes; guanidines and diguanidines;
pyridinaldimines; hydrazones; hydramides; nitriles; thioureas and
thioamides; ureas and biurets; monothio ligands; diketone ligands;
dithioacyl disulfides; tetrathioperoxydicarbonic diamides; (hexa-,
penta-, or tetra-) thioperoxydicarbonic acids and salts;
1,2-dithiolates; rhodanines; dithiocarbimates; (thio)xanthates;
S-(alkyl- or aryl-thio)thiocarboxylic acids and salts;
phosphinodithioformates; (thio)borates and (thio)boronates;
(thio)arsonic acids and salts; (thio)antimonic acids and salts;
phosphine and arsine sulfides or oxides; beta-hydroxyketones and
aldehydes; squaric acids and salts; carbamates and carbimates;
carbazates; imidosulfurous diamides; sulfurdiimines; thiocarbonyl
and mercapto oximes; 2-nitrothiophenols; 2-nitrilo(thio)phenols;
acylcyanamides; imidates; 2-amidinoacetates; beta-ketoamines;
3-aminoacrylamides and 3,3-diaminoacrylamides; 3-aminoacrylic acids
and salts and 3-hydroxy-3-aminoacrylic acids and salts;
2-nitroanilines; amine and diazine N-oxides; hydrazides and
semicarbazides; (amino- or imino-)aryl phosphines; (thio- or
hydroxy-)aryl phosphines; arsines; five- or six-membered
heterocyclic rings containing one arsenic atom optionally having
additional arsenic binding sites;(two- to six-)membered arsenic
macrocyclics; selenoethers; five- or six-membered heterocyclic
rings containing one or two selenium atoms optionally having
additional selenium binding sites; (two- to six-)membered selenium
macrocyclics; 1,3-diselenoketones; 1,1-diselenolates;
diselenocarbamates; selenophosphoric acids and salts;
selenocarbonates; cyanide, isocyanide, and cyanamide ligands;
nitrosyl and nitrite ligands; azide ligands; thiolates and
selenolates; (thio)cyanate ligands; diene or bicyclic or tricyclic
hydrocarbon ligands; and carbonyl, halogen, or hydroxo ligands; and
combinations thereof; and wherein the solubility in water of the
cobalt/valence stabilizer complex is decreased by the addition of a
substituent group on the organic valence stabilizer, the
substituent group selected from nitro groups (--NO.sub.2),
peffluoroalkyl groups (--C.sub.xF.sub.2x+1), perchloroalkyl groups
(--C.sub.xCl.sub.2x+1), nitramine groups (.dbd.N--NO.sub.2),
thioketone groups (.dbd.C.dbd.S), sulfenyl halide groups (--S--X),
and sulfur dihaloimide groups (--N.dbd.SX.sub.2), and combinations
thereof.
71. A conosion-inhibiting conversion coating comprising cobalt,
wherein the cobalt is trivalent cobalt, or tetravalent cobalt, or
combinations thereof, and a valence stabilizer combined to form a
cobalt/valence stabilizer complex wherein the valence stabilizer is
an organic valence stabilizer selected from monoamines; diamines;
triamines; tetraamines; pentamines; hexamines; five- or
six-membered heterocyclic rings containing one to four nitrogen
atoms optionally having additional nitrogen, sulfur, or oxygen
binding sites; five- or six-membered heterocyclic rings containing
one or two sulfur atoms and having additional nitrogen binding
sites; five- or six-membered heterocyclic rings containing one or
two oxygen atoms and having additional nitrogen binding sites;
(two-, three-, four-, six-, eight-, or ten-)membered nitrogen,
nitrogen-sulfur, or nitrogen-oxygen macrocyclics; macrocyclic
oligothioketones or dithiolenes; diazenes; thio-, amido-, or
imido-derivatives of hypophosphoric, phosphoric, or diphosphoric
acids and salts; azo compounds, triazenes, formazans, azines,
hydrazones, or Schiff Bases containing at least two azo, imine, or
azine groups; azo compounds, triazenes, formazans, azines,
hydrazones, or Schiff Bases with ortho-(for aryl) or alpha- or
beta-(for alkyl) substitution; oximes; amidines and imido
compounds; dithio ligands; amides; amino acids; N-(thio)acyl
7-aminobenzylidenimines; (thio)hydroxamates; alpha- or
ortho-aminothio(di)carboxylic acids and salts;
(thio)semicarbazones; (thio)acyl hydrazones; (thio)carbazones;
silylaminoalcohols; thioalkyl amines and imines; hydroxyalkyl
imines; (thio)aryl amines and imines; guanylureas; guanidinoureas;
2-nitrosophenols; 2-nitrophenols; N-nitrosohydroxylamines;
1,3-monothioketones; monothiomalonamides; 2-thioacylacetamides;
2-acylthioacetamides; dithiodicarbonic diamides;
trithiodicarboxylic acids and salts; monothiocarbamates;
monothioethers; dithioethers; trithioethers; tetrathioethers;
pentathioethers; hexathioethers; disulfides; monophosphines;
diphosphines; triphosphines; tetraphosphines; pentaphosphines;
hexaphosphines; five- or six-membered heterocyclic rings containing
one or two sulfur atoms optionally having additional sulfur,
oxygen, or phosphorus binding sites; five- or six-membered
heterocyclic rings containing one to three phosphorus atoms
optionally having additional phosphorus, nitrogen, oxygen, or
sulfur binding sites; five- or six-membered heterocyclic rings
containing one to four nitrogen atoms and having additional
phosphorus binding sites; five- or six-membered heterocyclic rings
containing one or two oxygen atoms and having additional sulfur or
phosphorus binding sites; (five-, seven-, or nine-)membered
nitrogen, nitrogen-sulfur, or nitrogen-oxygen macrocyclics; (two-
to ten-)membered sulfur, sulfur-oxygen, or sulfur-phosphorus
macrocyclics, not including oligothioketones or dithiolenes; (two-
to ten-)membered phosphorus, nitrogen-phosphorus, or
oxygen-phosphorus macrocyclics; thio-, amido-, or imido-derivatives
of phosphonic and diphosphonic acids and salts containing no sulfur
binding sites; amido-, or imido-derivatives of hypophosphoric,
phosphoric, or diphosphoric acids and salts containing no sulfur
binding sites; dithioperoxydiphosphoramides;
dithioperoxydiphosphoric acids and salts;
monothioperoxydiphosphoramides; monothioperoxydiphosphoric acids
and salts; monothiophosphoric acids; phosphoro(dithioperoxoic)
acids and salts; azo compounds, triazenes, formazans, azines, or
Schiff Bases; silylamines; silazanes; guanidines and diguanidines;
pyridinaldimines; hydrazones; hydramides; nitriles; thioureas and
thioamides; ureas and biurets; monothio ligands; diketone ligands;
dithioacyl disulfides; tetrathioperoxydicarbonic diamides; (hexa-,
penta-, or tetra-) thioperoxydicarbonic acids and salts;
1,2-dithiolates; rhodanines; dithiocarbimates; (thio)xanthates;
S-(alkyl- or aryl-thio)thiocarboxylic acids and salts;
phosphinodithioformates; (thio)borates and (thio)boronates;
(thio)arsonic acids and salts; (thio)antimonic acids and salts;
phosphine and arsine sulfides or oxides; beta-hydroxyketones and
aldehydes; squaric acids and salts; carbamates and carbimates;
carbazates; imidosulfurous diamides; sulfurdiimines; thiocarbonyl
and mercapto oximes; 2-nitrothiophenols; 2-nitrilo(thio)phenols;
acylcyanamides; imidates; 2-amidinoacetates; beta-ketoamines;
3-aminoacrylamides and 3,3-diaminoacrylamides; 3-aminoacrylic acids
and salts and 3-hydroxy-3-aminoacrylic acids and salts;
2-nitroanilines; amine and diazine N-oxides; hydrazides and
semicarbazides; (amino- or imino-)aryl phosphines; (thio- or
hydroxy-)aryl phosphines; arsines; five- or six-membered
heterocyclic rings containing one arsenic atom optionally having
additional arsenic binding sites;(two- to six-)membered arsenic
macrocyclics; selenoethers; five- or six-membered heterocyclic
rings containing one or two selenium atoms optionally having
additional selenium binding sites; (two- to six-)membered selenium
macrocyclics; 1,3-diselenoketones; 1,1-diselenolates;
diselenocarbamates; selenophosphoric acids and salts;
selenocarbonates; cyanide, isocyanide, and cyanamide ligands;
nitrosyl and nitrite ligands; azide ligands; thiolates and
selenolates; (thio)cyanate ligands; diene or bicyclic or tricyclic
hydrocarbon ligands; and carbonyl, halogen, or hydroxo ligands; and
combinations thereof; and wherein an electrostatic barrier layer of
the cobalt/valence stabilizer complex is increased by the addition
of a substituent group on the organic valence stabilizer, the
substituent group selected from ketones (.dbd.C.dbd.O), thioketones
(.dbd.C.dbd.S), amides (--C[.dbd.O]--NR.sub.2), thioamides
(--C[.dbd.S]--NR.sub.2), nitriles or cyano groups, (--CN),
isocyanides (--NC), nitroso groups (--N.dbd.O), thionitroso groups
(--N.dbd.S), nitro groups (--NO.sub.2), azido groups (--N.sub.3),
cyanamide or cyanonitrene groups (.dbd.N--CN), cyanate groups
(--O--CN), isocyanate groups (--N.dbd.C.dbd.O), thiocyanate groups
(--S--CN), isothiocyanate groups (--N.dbd.C.dbd.S), nitrosamine
groups (.dbd.N--N.dbd.O), thionitrosamine groups (.dbd.N--N.dbd.S),
nitramine groups (.dbd.N--NO.sub.2), thionitramine groups
(.dbd.N--NS.sub.2), carbonylnitrene groups (--CO--N),
thiocarbonylnitrene groups (--CS--N), sulfenyl halides (--S--X),
sulfoxides (.dbd.S.dbd.O), sulfones (.dbd.S[.dbd.O].sub.2),
sulfinyl groups (--N.dbd.S.dbd.O), thiosulfinyl groups
(--N.dbd.S.dbd.S), sulfenyl thiocyanato groups (--S--S--CN),
sulfenyl cyanato groups (--S--O--CN), sulfodjimine groups
(.dbd.S[.dbd.NH].sub.2), sulfur dihaloimido groups
(--N.dbd.SX.sub.2), sulfur oxide dihaloimido groups
(--N.dbd.S[.dbd.O]X.sub.2), aminosulfur oxide trihalide groups
(.dbd.N--S[.dbd.O]X.sub.3), sulfonyl azide groups
(--S[.dbd.O].sub.2N.sub.3), sulfonyl thiocyanate groups
(--S[.dbd.O].sub.2SCN), sulfonyl cyanate groups
(--S[.dbd.O].sub.2OCN), sulfonyl cyanide groups
(--S[.dbd.O].sub.2CN), halosulfonate groups (--S[.dbd.O].sub.2OX),
phosphonyl thiocyanate groups (--P[.dbd.O]OHSCN), phosphonyl
cyanate groups (--P[.dbd.O]OHOCN), and phosphonyl cyanide groups
(--P[.dbd.O]OHCN), and combinations thereof.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is related to commonly assigned U.S. patent
application Ser. No. 10/037,576, NON-TOXIC CORROSION-PROTECTION
PIGMENTS BASED ON COBALT, filed Jan. 4, 2002 by Sturgill et al. and
U.S. patent application Ser. No. 10/038,150, NON-TOXIC
CORROSION-PROTECTION RINSES & SEALS BASED ON COBALT, filed Jan.
4, 2002 by Sturgill et al., the disclosures of which are
incorporated herein by reference.
BACKGROUND OF THE INVENTION
This invention relates generally to compositions and methods for
the formation of protective, corrosion-inhibiting coatings on
metals, or other materials coated with metals, without the use of
chromium in the hexavalent oxidation state. More particularly, this
invention relates to non-toxic, corrosion-inhibiting conversion
coatings based on trivalent and tetravalent cobalt and methods of
making and using the same.
Metals like aluminum, zinc, magnesium, titanium, cadmium, silver,
copper, tin, lead, cobalt, zirconium, beryllium, or indium, their
alloys, or items coated with these metals, tend to corrode rapidly
in the presence of water due to their low oxidation-reduction
(redox) potentials or ease of oxide formation. Non-alloyed
specimens of these metals typically form a natural oxide film that
will protect them somewhat and reduce their overall rate of
corrosion. However, alloys of these metals are particularly
sensitive to corrosive attack. These materials also have a
significant problem with paint adhesion. The as-formed metal
surfaces are typically very smooth, and they tend to form weakly
bound surface oxides. The native oxides do not normally provide a
robust base on which subsequent paints can anchor themselves. These
metal alloys have many uses ranging from architectural adornments
to protective coatings on ferrous alloys to structural aerospace
components.
The 2000 and 7000 series of aluminum alloys are used throughout
military and civilian aircraft because of their high strength to
weight ratio. However, these aluminum alloys are very sensitive to
corrosive attack because their natural oxide layer offers only a
limited degree of protection. Materials with greater redox
potentials, such as steels or carbon fibers, in proximity to
aluminum alloys will promote corrosive attack in water by the
formation of a galvanic corrosion couple with the less-noble light
metal alloy.
Inhibiting the initiation, growth, and extent of corrosion is a
significant part of component and systems design for the successful
long-term use of metal objects. Uniform physical performance and
safety margins of a part, a component, or an entire system can be
compromised by corrosion.
One method to enhance the corrosion resistance of these alloys is
through the use of a conversion coating. A conversion coating is a
self-healing, corrosion-inhibiting layer formed during intentional
exposure to a chemically reactive solution. The conversion coating
process forms an adherent surface containing an integral corrosion
inhibitor with "throwing power" that can provide protection to
coating breaches. The metal is exposed to a compound that
chemically alters the surface and forms a coating that provides a
high degree of corrosion resistance. A chemical conversion coating
applied to the surface of a less-noble alloy can reduce the extent
and severity of aqueous corrosion, provide long-term property
stability, and extend the useful life of the object of
manufacture.
Conversion coatings incorporate a portion of the base metal and
form a mechanical, chemical, and electrostatic barrier to corrosive
attack. A critical feature of effective conversion coatings is
their ability to provide corrosion protection to the base metal in
the presence of a coating breach.
Anodization of a metal surface followed by "sealing" or "rinsing"
of the anodized metal does not constitute the formation of a
conversion coating in our usage. Anodization, the formation of a
porous oxide film on the metal, is achieved by the application of
an electrical potential to the metal. This oxide film must then be
"sealed", "washed", or "rinsed" in order to impart complete
corrosion protection. Typically, the corrosion protection afforded
by an anodized piece is due to the barrier oxide film. Conversion
coatings, however, grow an oxide coating on the metal without an
externally applied electrical potential. The protective film is
produced by a chemical redox reaction between the metal surface and
the conversion coating solution. The film is composed both of an
oxide and integral corrosion inhibitor species formed during
exposure to the conversion coating solution. A true conversion
coating therefore affords corrosion protection from an oxide
barrier film that has co-deposited oxidative corrosion inhibitor
species.
A conversion-coated surface may be left bare or afforded further
protection by the application of additional films or coatings.
Conversion coatings need to adhere to the substrate and should
result in a surface that will promote the formation of a strong
bond with subsequently applied coatings. Bonding with subsequently
applied coatings is a function of the morphology and chemical
composition of the conversion coating. Adhesion promoting surface
treatments may exhibit corrosion inhibiting characteristics.
Depending on the intended application, a conversion coating, as
described herein, may be considered to be an "adhesion promoter"
and vice versa.
Conversion coatings are usually formed by the application of a
conversion coating solution to a metal surface. The solution can be
applied by immersion, spray, fogging, wiping, or other means.
Hexavalent chromium has traditionally been used in the formation of
protective conversion coatings for aluminum, zinc, magnesium,
titanium, cadmium, silver, copper, tin, lead, cobalt, zirconium,
beryllium, indium, and their alloys. Compounds such as Alodine
1200.TM. (Henkel Co.) and Alumagold.TM. (Turco Co.) contain
hexavalent chromium as their main corrosion-inhibiting
compound.
Two generic types of hexavalent chromium coatings have been widely
used. The newer "gold" coatings are named for the faint gold tint
that the coatings have when they form on the surface of aluminum
alloys. The compositions and application procedures of these "gold"
hexavalent chromium conversion coating formulations are described
in United States military process specifications, as well as other
federal guidelines. Therefore, guidelines for the application of
these solutions to aluminum (MIL C-5541; MIL C-81706; MIL STD-171;
ASTM B-449), zinc (ASTM B-633; ASTM B-201; MIL C-17711; QQ Z-325a),
magnesium (MIL M-3171), cadmium (ASTM A-165; ASTM B-201; QQ
P-416b), silver (ASTM B-700; QQ S-365a), copper (ASTM B-281), and
tin (ASTM A-599; QQ-T-425a) are available. The common components to
these "gold" conversion coating baths are hexavalent chromium,
complex fluorides, and ferricyanide. Older "green" conversion
coatings containing hexavalent chromium have also been described,
and the color formed on aluminum alloys through the application of
these conversion coatings is a light green color. The "green"
formulations all contain hexavalent chromium, a fluoride, and an
acidic phosphate component. The major compositional difference
between the two is that the current "gold" formulation contains
ferricyanide and the older "green" formulations contain
phosphate.
Corrosion-resistant compositions have also been described which
contain hexavalent chromium, fluoride, and molybdic acid or
molybdates, rather than ferricyanide or phosphate. Tungstates and
vanadates have also been used in combination with hexavalent
chromium and fluoride. Hexavalent chromium formulations which do
not contain a fluoride source, and which contain borate ions
instead of ferricyanide or phosphate or molybdate have also been
described. Hexavalent chromium has also been used in combination
with stannates, oxalates, and tellurates. Finally, corrosion
protection of aluminum, magnesium, or zinc alloys has been achieved
through the use of hexavalent chromium, fluoride, and rare earth
compounds.
The variation in the type and amount of additional components such
as ferricyanide, phosphate, molybdate, and borate, etc., in
conversion coat formulations based on hexavalent chromium is
significant in light of the chemistry developed and presented in
the present invention. It is important to note that hexavalent
chromium conversion coatings which have nearly identical
formulations, except for one or more of the non-chromium
components, result in obvious differences on the applied metal
surface for a given alloy (such as "gold" and "green" coatings). It
is also important to note that differences in the composition of
aluminum alloys will influence the chemistry of the conversion
coating formed when only one hexavalent chromium conversion coat
composition is used.
Significant efforts have been made to replace chromium with other
metals for corrosion-inhibiting applications due to toxicity,
environmental, and regulatory concerns. Cobalt is one non-toxic,
non-regulated metal which has been considered as a chromium
replacement. Cobalt (like chromium) exhibits more than one
oxidation state (Co.sup.+2 and Co.sup.+3). In addition, the
oxidation-reduction potential of the Co.sup.+3--Co.sup.+2 couple is
comparable to the Cr.sup.+6--Cr.sup.+3 couple. For example, in acid
solution:
TABLE-US-00001 Co.sup.+3 + e => Co.sup.+2 +1.92 V Cr.sup.+6 + 3e
=> Cr.sup.+3 +1.36 V
A number of processes have been reported in the literature which
make use of cobalt in conversation coating bath solutions, as well
as general corrosion protection or coloring of the alloys. However,
the coatings formed by these processes provide only limited
protection and do not approach the benefit derived from the use of
hexavalent chromium.
The use of film-forming substances, such as polymers, silicates,
sol-gel, etc., which have no inherent oxidizing character, in
conversion coating solutions has been described in the literature.
The film formers may enhance short-term corrosion resistance by
functioning as a barrier layer. However, these films interfere with
substrate oxidation during the conversion coating process and
produce thin, incompletely anodized surfaces, resulting in poor
mechanical adhesion to the solution-deposited polymer film and to
later applied coatings. Restricting the formation of the oxide
layer that acts as a reservoir for the active corrosion inhibitor
yields a barrier film that is inhibitor starved. Barrier layers
lacking an active corrosion inhibitor have been demonstrated to be
capable of inhibiting corrosion only as long as the barrier is not
breached, as by a scratch or other flaw. Film formers can actually
enhance corrosion on a surface after failure due to the well known
effects of crevice corrosion. The addition of polymer during
conversion coating also produces a smooth coating which can reduce
subsequent paint adhesion, resulting in reduced long-term corrosion
protection.
The following references describe conversion coating processes
based on cobalt: PCT International Application Nos. WO 96/29,448,
WO 98/51,841, WO 96/21,753, WO 93/05,198, and S. African Patent No.
ZA 93/01,234 to Dolan; PCT International Application Nos. WO
96/05,335, WO 94/00,619, and European Patent Application Nos. EP
523,288, EP 458,020, EP 488,430, and U.S. Pat. Nos. 5,873,953,
5,411,606, 5,378,293, 5,298,092, and 5,551,994 to Schriever. These
specifications use additives that they term "bath stabilizers."
These chemical species are claimed to form more stable coordination
bonds with cobalt(III) cations than with cobalt(II) cations in the
aqueous conversion coating solution. Specifically, carboxylates,
hydroxyalkyl amines (aminoalcohols, such as triethanolamine), or
nitrito complexes are described in these specifications as being
added to the bath to retain trivalent cobalt in solution and to
stabilize concentrations during the coating process. These bath
stabilizers only treat and extend the service life of the
cobalt(III) in the conversion coating solution itself.
"Bath stabilizers" used in the manner of these specifications
reduce the formation and precipitation of Co.sup.+3-containing
solids during coating deposition. Bath stabilizers described in
these patents behave similar to masking agents for chemical
gravimetric analysis to keep unwanted compounds from precipitating.
They actually serve to starve the deposited coating of Co.sup.+3 by
shifting the equilibrium away from the formation of a
corrosion-inhibiting coating containing trivalent cobalt on a metal
surface to the trivalent cobalt remaining dissolved in the coating
bath. The compounds formed from the solutions described in these
specifications have lower structural stability in the coating, as
well as higher aqueous solubility, than if no bath stabilizer were
used at all. The art described in the specification and examples
herein shows that the solubilities of the formed compounds are
still too high to afford long-term corrosion protection.
A post-treatment rinse with a vanadate or tungstate solution is
used in PCT International Application Nos. WO 96/29,448 and WO
98/51,841 to Dolan, as well as PCT International Application No. WO
96/05,335 and U.S. Pat. No. 5,551,994 to Schriever. This rinse
seals the coating deposited from the solution, as described in
these specifications. Co.sup.+3-vanadate/tungstate complexes form
during these sealing treatments. These complexes are slightly
soluble and serve to enhance the corrosion resistance of the
deposited coating. However, the sealing step used in this art is
not an efficient method to treat the coating thickness or to
incorporate sparingly soluble Co.sup.+3 compounds into the coating
effectively. The effectiveness of the vanadate/tungstate sealing
step is also reduced because the bath stabilizers carried over from
the first solution increase the solubility of
Co.sup.+3-vanadate/tungstate complexes. Furthermore, the toxicity
of the conversion coatings is not reduced if pentavalent vanadium
is used in chrome-free compositions because the threshold limit
value (TLV) of both CrO.sub.3 and V.sub.2O.sub.5 is 0.05
mg/m.sup.3, and the permissible exposure limit (PEL) of both is 0.5
mg/m.sup.3.
These Schriever and Dolan coating processes also require the use of
elevated temperatures, especially for the sealing process (40 to
75.degree. C. being a typical range). Conversion coating processes
that take place at elevated temperatures (above room temperature)
can result in higher coating costs and increase the difficulty of
the coating application.
Accordingly, a need exists for improved corrosion-protection
conversion coatings composed of currently unregulated and/or
non-toxic materials which have an effectiveness, ease of
application, and performance comparable to coatings formed with
hexavalent chromium, and for methods of making and using the
same.
SUMMARY OF THE INVENTION
That need is met by the present invention which represents a
significant improvement in the formulation of non-toxic conversion
coatings through the use of trivalent cobalt. The conversion
coatings of the present invention inhibit corrosion to a higher
degree than any other known cobalt-based coatings. Moreover, the
coatings inhibit corrosion to a degree comparable to commercial
formulations based on hexavalent chromium. They do not require the
use of elevated temperatures, exotic materials, or application
methods.
The present invention utilizes `valency stabilization` of the
trivalent (or tetravalent) cobalt ion in the as-formed conversion
coatings to achieve corrosion resistance that is comparable to
hexavalent chromium. More specifically, in order to achieve a high
degree of corrosion resistance, a conversion coating can exhibit
the following characteristics: 1) The coating can contain an
oxidizing species. Oxidizing species serve two important functions
within the coating: a) they act to impede the flow of charged
species through the coating, therefore helping reduce the transport
of corrosion reactants, and b) if a scratch is formed in the
coating, these oxidizing species act to "repair" the breach by
oxidizing the underlying metal and quickly reforming an oxide
barrier. The effectiveness of oxidizing species is a function of
their individual oxidation-reduction potential, and the more highly
oxidized species exhibit greater corrosion protection. An
oxidation-reduction potential of approximately +0.80 V (at a pH of
0) appears to be the dividing line between inhibitors that offer
some corrosion protection and those that do not. The trivalent
cobalt ion, with an oxidation-reduction potential of +1.92 V (at a
pH of 0), is an exceptionally good oxidizing species. The hydroxyl
and oxygen liberated from water when trivalent cobalt is reduced
will oxidize ("passivate") nearby bare metal. 2) A "valence
stabilizer" for the trivalent cobalt can be employed to ensure that
the ion will not be reduced quickly to the divalent state in
solution or in the coating. The importance of stabilizing the
cobalt ion in its trivalent state in a solid precipitate was not
previously recognized as important to the formation of a conversion
coating. 3) The trivalent cobalt species formed in the coating can
be present as a "sparingly soluble" material. If the formed
trivalent cobalt species is too soluble, then it will be washed
away. If it is too insoluble, then insufficient trivalent cobalt is
available to inhibit corrosion. A trivalent cobalt species that
exhibits low solubility will not only fail to inhibit corrosion,
but can promote localized crevice corrosion and result in enhanced
corrosion rates. In order to form an effective conversion coating,
the trivalent cobalt compounds formed in the coating must be in a
"sparingly soluble" form. It is difficult to place specific
solubility values to these optimum "sparingly soluble" coating
materials because there appear to be several variables associated
with what makes an optimum coating material. It appears that if the
trivalent cobalt is incorporated in the coating in the form of a
trivalent cobalt/valency stabilizer complex, which exhibits a
solubility in water of between about 5.times.10.sup.-5 and about
5.times.10.sup.-2 moles per liter of trivalent cobalt, then
appreciable corrosion inhibition will be observed. Coatings that
incorporate stabilized trivalent cobalt compounds that fall outside
of this particular solubility range may also exhibit some corrosion
inhibition. For example, compositions with solubilities as high as
5.times.10.sup.-1 moles per liter or as low as 1.times.10.sup.-5
moles per liter of trivalent cobalt, at standard temperature and
pressure, exhibited some corrosion resistance, although not as
great as those compounds which fall within the optimum solubility
range. The degree of effectiveness will depend on the particular
compound itself. The solubility characteristics of the trivalent
cobalt in the conversion coatings must be controlled through the
use of stabilizer materials which form compounds that fall within a
desired solubility range. In this way, a "controlled release" of
trivalent cobalt can be achieved, much as a "timed release" of
hexavalent chromium is achieved in the "state-of-the-art" systems.
4) The "valence stabilizer" helps establish an electrostatic
barrier layer around the cation-stabilizer complex in aqueous
solutions. The nature and character of the electrostatic
double-layer surrounding the cation-stabilizer complex may be
controlled and modified by careful selection of stabilizer species.
Characteristics such as the electrical dipole moment and the
shape/conformation (for steric effects) of the stabilizer were
found to influence the performance of the conversion coating. In
general, the electrostatic double layer formed acts to protect the
cation from premature reaction with hydronium, hydroxide, and other
ions in solution. The formation of electrostatic barrier layers
also helps to impede the passage of corrosive ions through the
conversion coatings to the metallic surface.
This phenomena is exhibited in the hexavalent chromium systems,
wherein the highly charged hexavalent chromium is surrounded by
very polar ferricyanide ions. The orientation of the dipoles of the
ferricyanide ions with respect to the highly charged chromate ion
serves to attract additional layers of ions in the aqueous
solution. These ions form a protective shell around the
cation-stabilizer complex. 5) The coating material may also exhibit
ion exchange behavior towards alkali species. This optional
consideration is important for the formation of conversion coatings
which resist corrosion because alkali ions (especially sodium) are
notoriously corrosive towards alloys which contain metals such as
aluminum, magnesium, or zinc. The hexavalent chromium-ferricyanide
complex formed in the conventional systems also exhibits this ion
exchange phenomena.
The corrosion resistance of a number of aluminum alloys as tested
using both ASTM B-117 and ASTM G-85 has been enhanced through the
use of stabilized trivalent cobalt conversion coatings. Not only do
these optimized coatings retard corrosion to a higher degree than
other prior art trivalent cobalt baths, but their corrosion
resistance is comparable to that of hexavalent chromium systems.
Unlike the prior art, the trivalent cobalt conversion coatings of
the present invention do not require elevated temperatures for
their application, nor do they use materials which are as toxic as
the hexavalent chromium they are attempting to replace.
The valence stabilizers can be inorganic or organic. A multitude of
organic and inorganic stabilizer materials have been used.
In one aspect, the invention comprises a mechanistic and chemical
approach to the production of corrosion-resistant conversion
coatings using trivalent cobalt. This approach uses stabilizer
materials which form compounds with trivalent cobalt that are
sparingly soluble in aqueous solution, typically from about
5.times.10.sup.-2 to about 5.times.10.sup.-5 moles/liter of
trivalent cobalt. This solubility range provides a release of
trivalent cobalt at a rate sufficiently slow enough that protection
will be provided for an extended period of time and fast enough to
inhibit corrosion during conventional accelerated corrosion testing
methods such as ASTM B-117 and ASTM G-85 for conversion coatings.
Compounds that fall slightly outside of this solubility range (as
high as 5.times.10.sup.-1 to as low as 1.times.10.sup.-5
moles/liter of trivalent cobalt at standard temperature and
pressure) may also prove to be effective conversion coatings under
certain conditions. However, compounds that exhibit aqueous
solubilities far outside of the target range are unlikely to be
effective corrosion inhibitors. The solubility of the formed
trivalent cobalt compounds plays a significant role in the
effectiveness of the formed coating. Solubility control can be
achieved using organic or inorganic stabilizer materials.
In another aspect, the invention is the achievement of
corrosion-resistant conversion coatings using trivalent cobalt.
This approach also utilizes stabilizer materials, which form
compounds that exhibit dipoles so as to form electrostatic barrier
layers composed of ions, such as hydronium (H.sub.3O.sup.+) or
hydroxide (OH.sup.-). The formation of these barrier layers through
the use of stabilizer materials can be achieved using organic or
inorganic materials.
In an optional aspect, the invention is the achievement of
corrosion-resistant conversion coatings using trivalent cobalt by
the use of stabilizer materials, which form compounds that exhibit
ion exchange behavior towards alkali ions. The formation of this
ion exchange behavior can be achieved through the use of organic or
inorganic materials.
In another optional aspect, the invention is the achievement of
corrosion-resistant conversion coatings using preparative agents in
conjunction with the cobalt to strip uncontrolled native oxide
layers on the work piece surface, as well as to control the rate of
coating deposition. Typical preparative agents for the formation of
trivalent cobalt conversion coatings are fluorides and
fluorine-containing chemicals. Acidic species or other halides such
as chlorides, bromides, and iodides can be used, but are less
effective than fluorides as preparative agents.
In another optional aspect, the invention is the achievement of
superior corrosion-resistant conversion coatings by allowing the
deposited trivalent cobalt-containing coating to reach a desired
thickness and/or morphology in order to maximize adhesion to the
work piece, as well as maximizing adhesion of subsequently-applied
paint films to the conversion coating. Ideally, the thickness of
the formed trivalent cobalt conversion coating should be
approximately 200 nanometers. The minimum thickness allowable for a
satisfactory pinhole-free trivalent cobalt conversion coating is
approximately 25 nanometers, and the maximum allowable thickness is
approximately 10,000 nanometers. The morphology of the formed
conversion coating should be sufficient to allow for paint films to
adhere to it. A "mud crack" or "honeycomb" morphology is
typical.
Accordingly, it is an object of the present invention to provide
non-toxic corrosion-protection conversion coating baths based on
trivalent cobalt and methods of making and using the same. These
and other objects and advantages of the present invention will
become apparent from the following detailed description and
claims.
DETAILED DESCRIPTION OF THE INVENTION
A) Starting Materials
Five general starting materials can be used for the conversion
coating baths of the present invention. These include: a cobalt
source; an oxidation source (optional); a preparation agent source
(optional); a valence stabilizer source; and additional solubility
control agents (optional). These materials may be included as neat
compounds in the conversion coating bath, or may be added to the
conversion coating bath as already-prepared solutions. Further
enhancements to the formed coating may be imparted through the use
of additional starting materials. Foremost among these are agents
to improve the color-fastness of the coating.
1) Cobalt Source
a) Trivalent Cobalt
The cobalt precursor compounds can be almost any cobalt compound in
which the cobalt is in either the divalent or trivalent oxidation
state. Water-soluble precursors are typically used. Examples of
inorganic divalent cobalt precursor compounds include, but are not
restricted to: cobalt nitrate, cobalt sulfate, cobalt perchlorate,
cobalt chloride, cobalt fluoride, cobalt bromide, cobalt iodide,
cobalt bromate, cobalt chlorate, and complex fluorides such as
cobalt fluosilicate, cobalt fluotitanate, cobalt fluozirconate,
cobalt fluoborate, and cobalt fluoaluminate. Examples of
organometallic divalent cobalt precursor compounds include, but are
not restricted to: cobalt formate, cobalt acetate, cobalt
propionate, cobalt butyrate, cobalt benzoate, cobalt glycolate,
cobalt lactate, cobalt tartronate, cobalt malate, cobalt tartrate,
cobalt citrate, cobalt benzenesulfonate, cobalt thiocyanate, and
cobalt acetylacetonate. Complex divalent cobalt precursor compounds
include, but are not limited to, ammonium cobalt sulfate, ammonium
cobalt nitrate, ammonium cobalt chloride, and ammonium cobalt
bromide.
The cobalt precursor may also be a compound in which the cobalt is
already in the trivalent oxidation state. Examples of these
compounds include, but are not restricted to: hexaaminecobalt
chloride, hexaaminecobalt bromide, hexaaminecobalt nitrate,
pentaaminecobalt chloride, pentaaminecobalt bromide,
pentaaminecobalt nitrate, lithium cobaltinitrite, sodium
cobaltinitrite, tris(ethylenediamine)cobalt chloride,
tris(ethylenediamine) cobalt nitrate, bipyridine complexes of
trivalent cobalt, phenanthroline complexes of trivalent cobalt,
cobalt (III) acetylacetonate, cobalticarbonates, cobalt (III)
acetate, cobalt (III) chloride, and cobalt (III) sulfate.
While trivalent cobalt precursor compounds can be used, they are
not recommended for the following reasons: 1) their cost is several
orders of magnitude higher than divalent cobalt precursors; 2) in
some instances (e.g., cobaltinitrite or cobalticarbonate compounds)
they generate large quantities of gas (NO.sub.2 or CO.sub.2) when
placed into acidic solutions; and 3) they lead to lower corrosion
protection in the formed coatings because they are stabilized with
additional materials to improve their solubility in water.
It may not be necessary to add a separate cobalt source for these
conversion coating solutions if a cobalt-containing alloy is to be
treated. The preparative agent contained within these conversion
coating formulations can dissolve some of the cobalt in the
substrate. This will result in divalent cobalt ions being present
in the coating solution. A suitable oxidizer can then oxidize the
divalent cobalt to the necessary trivalent oxidation state during
or after coating deposition.
b) Tetravalent Cobalt
The tetravalent cobalt ion (Co.sup.+4) is an even better oxidizing
species than Co.sup.+3. It has a radius of 0.053 nanometers,
carries a charge of +4, and has a redox potential of over 2.0V.
However, it has a correspondingly lower stability both in and out
of solution. Therefore, valence stabilization of this ion is
required in order to use it effectively in a conversion coating.
Its very large redox potential makes it prone to rapid reduction,
and few materials will effectively valence stabilize it in a
sparingly soluble complex, which make its routine application
problematic. Tetravalent cobalt can be made using chemical or
electrolytic oxidation, as can trivalent cobalt.
The presence of both trivalent and tetravalent cobalt in these
coatings can be determined by their magnetic behavior. A
combination of Co.sup.+3 and Co.sup.+4 is reportedly paramagnetic.
The difficulty of its formation or stabilization should not
preclude the use of tetravalent cobalt in some conversion coatings.
While it is not a typical species because of these difficulties,
tetravalent cobalt can be incorporated either alone or in
conjunction with trivalent cobalt by using tailored valence
stabilizers.
2) Oxidation Source
Oxidizers serve two important functions within the coating: 1) they
act in cooperation with the stabilizer to impede the flow of ionic
species through the coating, therefore minimizing charge transport,
and 2) if a scratch is formed in the coating, these oxidizing
species act to repair the breach by oxidizing the metal in the
presence of water, and quickly reforming an oxide barrier. The
effectiveness of the oxidizing species is a function of its
individual oxidation-reduction potential, with more highly oxidized
species exhibiting greater corrosion protection.
In order to provide adequate oxidation potential in the conversion
coating solution, especially if divalent cobalt compounds are
utilized as precursors, an oxidizing species must also be included
as a starting material. Additional amounts of oxidizer may be added
to help control and maintain a desired amount of Co.sup.+3 in the
conversion coating solution by reoxidizing Co.sup.+3 that has been
reduced. Because of the high potential of the redox reaction
required to oxidize divalent cobalt to trivalent (or tetravalent)
cobalt, strong oxidizers must be utilized for this purpose. These
oxidizers may be gaseous, liquid, or solid in form. Solid oxidizers
are typically used for this application due to ease of handling and
reagent measurement. Other starting materials (cobalt source,
fluoride source, stabilizer source) will frequently also be solids.
Liquid oxidizers may also be used, but handling and accurate
process metering have proven difficult. Gaseous oxidizers may be
the most cost effective and chemically efficient on a large scale,
but are also the most problematic due to handling and venting
concerns.
Examples of oxidizers suitable for the purpose of producing and
maintaining the cobalt ion in the trivalent charge state include,
but are not restricted to: peroxides and peroxo compounds
(including superoxides, persulfates, perborates, pernitrates,
perphosphates, percarbonates, persilicates, peraluminates,
pertitanates, perzirconates, permolybdates, pertungstates,
pervanadates, and organic peroxyacid derivatives), ozone,
hypochlorites, chlorates, perchlorates, nitrates, nitrites,
vanadates, iodates, hypobromites, chlorites, bromates,
permanganates, periodates, and dissolved oxygen. Both inorganic and
organic derivatives of these compounds may be used. Typical
oxidizers are peroxides, persulfates, perbenzoates, periodates,
bromates, hypochlorites, and gaseous dissolved oxygen, including
the oxygen content of air. In general, any inorganic, organic, or
combination species that has an oxidation potential of +1.5V or
higher (at a pH of 1) will be capable of oxidizing divalent cobalt
to the trivalent, or in some instances the tetravalent, oxidation
state.
Oxidation of the cobalt to the trivalent state may also be achieved
in the conversion coating solution through electrolytic means. In
most instances, however, this approach may not be economically
feasible due to the large energy costs associated with electrolytic
oxidation. Chemical oxidation, such as that described above,
currently offers the lowest-cost means to achieve oxidation of the
cobalt to the trivalent state.
It is also possible to deposit divalent cobalt in a conversion
coating, and then apply a second solution containing an oxidizer to
oxidize divalent cobalt to trivalent cobalt. This, however, is less
typical because the percentage of deposited cobalt that will be in
the trivalent state will be less than if trivalent cobalt were
deposited directly.
In the conversion coating solutions based on hexavalent chromium,
oxidation sources are added to speed up the conversion coating
process. Hence, they are termed "accelerators" in the hexavalent
chromium formulations. Because the application of an acid (i.e., a
conversion coating solution) to an electronegative metal will
result in the formation of hydrogen gas, cathodic areas on the
treated metal will be partially blocked from further coating
formation. Oxidizers ("accelerators") act to eliminate hydrogen gas
formation, thereby minimizing its barrier effect, and hence
accelerating the overall deposition rate. It is for this reason
that it is also desirable to have oxidizers in the initial
conversion coating bath.
3) Preparative Agent Source
Uniform, adherent, low-defect film growth can be achieved if the
conversion coat is deposited on a suitably prepared surface.
Removing pre-existing "wild" native oxides is the first step to
achieve the formation of high-quality conversion coatings. A
preparative agent is any material that removes (dissolves and
breaks up) preexisting surface oxides and provides a bare metal
surface on which to deposit the conversion coating. The hexavalent
chromium formulations term these materials "activators" or "surface
etchants." The breakup and dissolution of the surface oxide in
solution produces a bare unprotected metal suited for controlled
oxidation, textures the surface, and encourages precipitation of
the conversion coat compounds at the metal surface by locally
raising the solution pH.
Fluoride acids and salts work especially well as preparative agents
in conversion coating baths. The complex fluoride anions
hexafluorozirconate (ZrF.sub.6.sup.-2) and hexafluorotitanate
(TiF.sub.6.sup.-2) are superior fluoride sources for this
application. Hexafluorosilicates (SiF.sub.6.sup.-2) can be used,
but they result in a reduced level of subsequent corrosion
protection. The potassium, lithium, sodium, and ammonium salts of
these anions work especially well for this application, with
potassium performing the best.
Other complex fluorides, including, but not restricted to,
fluoroaluminates (e.g., AlF.sub.6.sup.-3 or AlF.sub.4.sup.-1),
fluoroborates (e.g., BF.sub.4.sup.-1), fluorogallates (e.g.,
GaF.sub.4.sup.-1) fluoroindates (e.g., InF.sub.4.sup.-1),
fluorogermanates (e.g., GeF.sub.6.sup.-2), fluorostannates (e.g.,
SnF.sub.6.sup.-2), fluorophosphates (e.g., PF.sub.6.sup.-1),
fluoroarsenates (e.g., AsF.sub.6.sup.-1), fluoroantimonates (e.g.,
SbF.sub.6.sup.--1), fluorobismuthates (e.g., BiF.sub.6.sup.-1),
fluorosulfates (e.g., SF.sub.6.sup.-2), fluoroselenates (e.g.,
SeF.sub.6.sup.-2), fluorotellurates (e.g., TeF.sub.6.sup.2 or
TeOF.sub.5.sup.-1), fluorocuprates (e.g., CuF.sub.3.sup.-1 or
CuF.sub.4.sup.-2), fluoroargentates (e.g., AgF.sub.3.sup.-1 or
AgF.sub.4.sup.-2), fluorozincates (e.g., ZnF.sub.4.sup.-2),
fluorohafnates (e.g., HfF.sub.6.sup.-2), fluorovanadates (e.g.,
VF.sub.7.sup.-2), fluoroniobates (e.g., NbF.sub.7.sup.-2),
fluorotantalates (e.g., TaF.sub.7.sup.-2), fluoromolybdates (e.g.,
MoF.sub.6.sup.-3), fluorotungstates (e.g., WF.sub.6.sup.-1),
fluoroyttrates (e.g., YF.sub.6.sup.-3), fluorolanthanates (e.g.,
LaF.sub.6 .sup.3), fluorocerates (e.g., CeF.sub.6 .sup.3 or
CeF.sub.6.sup.-2), fluoromanganates (e.g., MnF.sub.6.sup.-2),
fluoroferrates (e.g., FeF.sub.6.sup.-3), fluoronickelates (e.g.,
NiF.sub.6.sup.-2), and fluorocobaltates (e.g., CoF.sub.6.sup.-2)
are also suitable fluoride sources, but these offer even less
corrosion protection than hexafluorosilicates. Water-soluble
potassium, sodium, lithium, or ammonium salts of these anions are
typical.
Simple inorganic fluorides such as potassium fluoride (KF),
potassium hydrogen fluoride (KHF.sub.2), sodium fluoride (NaF),
sodium hydrogen fluoride (NaHF.sub.2), lithium fluoride (LiF),
lithium hydrogen fluoride (LiHF.sub.2), ammonium fluoride
(NH.sub.4F), ammonium hydrogen fluoride (NH.sub.4HF.sub.2), and
even hydrofluoric acid solutions (HF) can also be used as a
fluoride source. By analogy, organic compounds that provide a ready
supply of aqueous fluoride ions will likewise serve as adequate
fluoride sources.
Other halide species, such as chlorides (Cl.sup.-), bromides
(Br.sup.-), and iodides (I.sup.-) can also function as preparative
agents, although their efficiency in stripping the surface oxide
will not be as great as the fluorides. Inorganic or organic
compounds that release chloride, bromide, or iodide anions can
function as preparative agents, as can a number of complex
chlorides and bromides that are similar to those described for the
fluorides. By analogy, complex hexachlorozirconates
(ZrCl.sub.6.sup.-2), hexachlorotitanates (TiCl.sub.6.sup.-2), and
hexachlorosilicates (SiCl.sub.6.sup.-2) should function better than
other chloride sources, and analogous complex bromide and iodide
sources will function better than other bromides and iodides.
Acidic species, such as nitric acid, sulfuric acid, phosphoric
acid, pyrophosphoric acid, hydrochloric acid, perchloric acid,
hydrobromic acid, hydriodic acid, iodic acid, periodic acid,
disulfuric acid, selenic acid, telluric acid, polyphosphoric acid,
cyclophosphoric acid, boric acid, vanadic acid, molybdic acid,
tungstic acid, carboxylic acids, phosphonic acids, and sulfonic
acids can also function as preparative agents. Of these, nitric
acid is the most useful as a preparative agent.
Although it is less desirable, hydroxides can also function as
preparative agents. For example, under high pH conditions zinc and
aluminum are known to dissolve in water, through the formation of
zincate or aluminate anions. The use of hydroxides such as sodium,
potassium, lithium, or ammonium derivatives will result in this pH
rise.
Changes in the concentrations of the fluoride components also had
significant effects upon the character of the deposited coating. It
was found that the corrosion resistance of the formed coating was
reduced if the fluoride concentration in solution came near or
exceeded its solubility in water. Craters form in the coating,
apparently caused by excess back etching of deposited oxides. The
concentration of fluoride also appears to influence the thickness
of the formed coating. The substrate metal remains bright and shiny
at very low fluoride concentrations. These effects were found to
begin when the ratio of fluoride ions to cobalt ions in the coating
solution dropped below 0.05.
Fluoride species with different alkali metals appeared to have
negligible effect upon the coating or its corrosion resistance. The
use of lithium did not result in any improvement in corrosion
resistance. Changes in the fluoride's associated alkali metals
(e.g., K.sub.2ZrF.sub.6, Na.sub.2ZrF.sub.6) did alter the
solubility of fluoride in solution and so control the amount of
fluoride available to etch the metal surface.
If a preparative agent is not included in the conversion coating
bath, then the "wild" native oxides must be removed by some other
process prior to the application of the conversion coating.
4) Valence Stabilizers
Corrosion resistance comparable to that of hexavalent chromium can
be achieved by the use of valence stabilized trivalent or
tetravalent cobalt ions in the conversion coating solutions.
Valence stabilization has not been recognized previously as an
important consideration in the development of effective corrosion
inhibiting conversion coats. A variety of inorganic and organic
stabilizers are available that can control such properties as
solubility, mobility, ion exchange, and binder compatibility. The
stabilizer complex can also act as an ion-exchange host and/or trap
for alkali or halide ions in solution.
Cobalt is effective as an oxidation corrosion inhibitor if it can
be supplied in sufficient quantities in the trivalent or
tetravalent charge state when brought into contact with unprotected
bare metal. The characteristics of the Co.sup.+3 ion which are
relevant to its use in conversion coating applications include: 1)
its valence is fairly stable in solution but is less stable on
drying, 2) its compounds typically have large aqueous solubilities,
3) it is more stable in acidic or neutral pH aqueous solutions than
in basic solutions, and 4) its radius of 0.061 nanometers is
slightly larger than the 0.044 nanometers of the hexavalent
chromium ion, and so it will have a correspondingly lower charge
density (electrostatic field) per ion.
The need for "valence stabilization" of trivalent (or tetravalent)
cobalt for corrosion inhibition has been indirectly noted in the
general corrosion literature. Corrosion inhibition behavior of
nitrogen-containing organics such as aniline or pyridine has been
reported to be enhanced with the addition of cobalt. The exact
nature of this "synergistic enhancement" has never been adequately
explained. These "synergistic" mixtures of nitrogen-containing
organics and cobalt have also been described as being
"oxygen-scavengers", and the organics are frequently observed to
"chemisorb" onto the substrate piece being protected.
This enhancement can be explained by our "valence stabilization"
model of corrosion inhibition by trivalent (or tetravalent) cobalt.
Nitrogen-containing organics and cobalt result in the formation of
an organometallic complex where the central cobalt ion can be
stabilized in a higher oxidation state. The observed
"oxygen-scavenging" phenomenon associated with dissolved oxygen in
aqueous solutions is easily explained by the oxidation of
stabilized divalent cobalt to the trivalent state. "Sparingly
soluble" Co.sup.+3 complexes containing these organics are
responsible for the corrosion-inhibiting activity, and these
organics will appear to be "adsorbed" or "chemisorbed" from
solution onto the metal piece being protected due to
precipitation.
As noted in the Summary of the Invention, the valence stabilizer
serves a number of important functions in the establishment of a
successful conversion coating. First, the valence stabilizer, when
used with trivalent cobalt, must result in a "sparingly soluble"
Co.sup.+3-valence stabilizer complex. Although the exact solubility
of this complex can be slightly modified through the incorporation
of different cations or anions (either through the dissolution of
the coated metal, or the subsequent treatment by additional
solubility control agents), appreciable corrosion inhibition will
be observed if the trivalent cobalt is incorporated in the
conversion coating as a Co.sup.+3-stabilizer complex that exhibits
a solubility in water of between about 5.times.10.sup.-5 moles per
liter and about 5.times.10.sup.-2 moles per liter of available
Co.sup.+3. Therefore, any material (inorganic or organic) in the
coating bath which complexes with trivalent cobalt and results in
the formation of a Co.sup.+3-containing complex which exhibits
solubilities within or near this solubility range can serve as a
valence stabilizer for trivalent cobalt.
Conversion coatings which incorporate stabilized trivalent cobalt
compounds that fall outside this particular solubility range may
exhibit some degree of corrosion inhibition and may be effective
conversion coatings under certain circumstances. Although not as
effective as those compounds within the optimum solubility range,
compositions with solubilities as high as 5.times.10.sup.-1 moles
per liter or as low as 1.times.10.sup.-5 moles per liter of
trivalent cobalt, at standard temperature and pressure (about
25.degree. C. and about 760 Torr), exhibited some corrosion
resistance. For example, in situations where the substrate metal
pieces are exposed to environments which require much more
immediate corrosion exposure (e.g., sudden immersion in seawater),
adequate corrosion protection can be achieved through the formation
of a trivalent cobalt compound which exhibits a higher solubility
in water (e.g., 5.times.10.sup.-1 to 5.times.10.sup.-3 moles/liter
trivalent cobalt). In this way, a more "immediate" release of
protective trivalent cobalt ions can be achieved, although the
trivalent cobalt will be depleted faster from the coating.
Trivalent cobalt solubilities that are lower than this optimum
range (e.g., 1.times.10.sup.-5 to 1.times.10.sup.-3 moles/liter of
trivalent cobalt) may be desirable for some situations (e.g., in
nearly pure water with low aeration rates). However, compounds that
exhibit solubilities far outside the target range are unlikely to
be effective corrosion inhibitors.
The solubility characteristics of the trivalent cobalt in the
conversion coatings must be controlled with stabilizer materials
that form compounds within the desired solubility range. The exact
solubility will be strongly dependent on the application of the
conversion coating and net aqueous solubility of overlying paints
and coatings. The formation of conversion coatings with the proper
release rate of Co.sup.+3 ions is problematic because of the
instability of Co.sup.+3 out of solution. Trivalent cobalt
compounds, such as acetate, sulfate, acetylacetonate, and hexaamine
chloride, are generally too soluble to serve as effective corrosion
inhibitors if incorporated into a conversion coating. Oxides and
hydroxides of Co.sup.+3 are much too insoluble in water to serve
effectively as corrosion inhibitors in a conversion coating.
The key to providing a useful source of trivalent cobalt at a metal
surface is the creation of a sparingly soluble compound in which
the Co.sup.+3 ion is shielded from premature reduction during and
after conversion coating formation. The assembly of a protective
shell around the highly charged Co.sup.+3 and its associated oxygen
and hydroxyl species can help control the rate at which the cobalt
is reduced and its oxygen is released. Proper selection of
materials for forming the protective shell will allow solubility
tailoring of the entire assembly to its intended application
environment. Valence stabilizers are materials that, when
assembled, modify the rate of reduction and the solubility of the
Co.sup.+3 ion.
The electrostatic character of the complex can also be considered
in creating a Co.sup.+3 stabilizer complex with optimal corrosion
resistance. Valence stabilizers can also contribute to the
development of a substantial electrostatic double layer. An
electrostatic double layer of polar or charged species such as
hydronium (H.sub.3O.sup.+) or hydroxide (OH.sup.-) ions surrounding
the stabilized cobalt complex will help control cobalt reduction
and solubility and enhance the barrier properties of the conversion
coating. Valence stabilizers which form sparingly soluble cobalt
complexes with enhanced electrostatic double layers will maximize
the corrosion-inhibiting character of the conversion coating.
The trivalent cobalt ion is slightly larger than the hexavalent
chromium ion, with less charge density over the surface of the ion.
Therefore, the valence stabilizers for Co.sup.+3 must be more
efficient in the establishment of dipole moments than the
ferricyanide ion so that comparable corrosion resistance can be
achieved in relation to the state of the art Cr.sup.+6-ferricyanide
compositions. Valence stabilizers which have a comparable dipole
moment to ferricyanide, or which exhibit even less of a dipole
moment than ferricyanide can also function as valence stabilizers,
but the resultant corrosion resistance of the conversion coatings
will, in all probability, be less than for the current commercial
hexavalent chromium-based conversion coatings.
Large spheres of hydration around corrosion inhibitors can act as
electrostatic and physical barriers to the passage of large
corrosive ions such as Cl.sup.- and SO.sub.4.sup.-2 through the
coating to the metal surface. The size of the electrostatic double
layer is a function of the electrostatic potential at the complex
surface and is inversely proportional to the ionic strength of the
surrounding solution. Compounds that can carry a charge, have a
natural electrostatic dipole, or can have a dipole induced, will
likely form an electrostatic double layer in aqueous solution.
However, these compounds do not normally act as corrosion
inhibitors because they have not been optimized for that
purpose.
Optionally, the incorporation of the valence stabilizer (inorganic
or organic) should result in the formation of a Co.sup.+3-valence
stabilizer compound which exhibits ion exchange behavior towards
alkali ions. As noted in the Summary of the Invention, this is not
a requirement of the Co.sup.+3-valence stabilizer complex, but it
is a desirable characteristic for enhanced corrosion resistance.
Some existing state of the art chromium systems exhibit this
phenomena, but conversion coating compounds that do not exhibit
this phenomena have been successfully demonstrated to inhibit
corrosive attack.
Cobalt coordination chemistry, which has been the subject of
numerous scientific studies for almost 100 years, identifies
chemical binding preferences, structure stability, and physical
properties of the resulting compounds. Producing effective
Co.sup.+3-valence stabilizer complexes requires understanding the
electrostatic and structural influence of candidate species on the
complex. Stabilizers can be designed that result in cobalt
compounds with the necessary physical, electrical, and chemical
properties to form corrosion inhibitors with this information.
Property tailoring can also take place through selection of
specific anions or cations bound to the Co.sup.+3-valence
stabilizer coordination complex.
The functional anatomy of inorganic stabilizers is simple because
of the limited number of atoms and structural arrangements involved
in their formation. The anatomy of organic stabilizers is not as
simple. An organically stabilized cobalt complex may have one or
more organic ligands that may have one or more bonding sites that
can interact with the Co.sup.+3 ion/oxide cluster. The bonding
groups can be the same or different atoms or functional groups on
an individual or a variety of ligands. An organic stabilizer ligand
can be modified in an unlimited number of ways to tailor its
physical behavior with respect to such properties as chemical
reactivity, solubility, electrostatic and polar character, and
functional behavior.
The stability of the Co.sup.+3-valence stabilizer complex is
strongly influenced by the charge, polarity sign, and degree of
polarizability of specific binding sites. Factors influencing
compound stability include: 1) ion-pair interactions for charged
ligands and Co.sup.+3, 2) ion-dipole and ion-induced dipole
interactions for neutral ligands, 3) hydrogen bonding, and 4) the
hard-soft acid-base (HSAB) rules convention of coordination
chemistry. HSAB rules help identify functional groups on ligands
that might be effective as binding sites. Optimum binding for
organic valence stabilizers to Co.sup.+3 will involve ligands with
soft bonding species such as those that contain sulfur or
phosphorus. Certain coordination complexes of the hard base
nitrogen are also effective for binding with Co.sup.+3. HSAB rules
can also help identify groups that might provide a degree of
polarization to the stabilizer because of their large dipole
moments.
The nature of bonding between the Co.sup.+3 ion/oxide cluster and
the stabilizer ligand can be altered by using a substituent group
to modify the stabilizer. Specific interactions between the ligand
and Co.sup.+3 can be tailored by substituent group selection,
coupled with altering the size or geometry of the complexing
ligand. For example, some substituent groups have large dipole
moments associated with them, which will increase the electrostatic
barrier layers associated with the cobalt/valence stabilizer
complexes. These include: ketones (.dbd.C.dbd.O), thioketones
(.dbd.C.dbd.S), amides (--C[.dbd.O]--NR.sub.2), thioamides
(--C[.dbd.S]--NR.sub.2), nitriles or cyano groups, (--CN),
isocyanides (--NC), nitroso groups (--N.dbd.O), thionitroso groups
(--N.dbd.S), nitro groups (--NO.sub.2), azido groups (--N.sub.3),
cyanamide or cyanonitrene groups (.dbd.N--CN), cyanate groups
(--O--CN), isocyanate groups (--N.dbd.C.dbd.O), thiocyanate groups
(--S--CN), isothiocyanate groups (--N.dbd.C.dbd.S), nitrosamine
groups (.dbd.N--N.dbd.O), thionitrosamine groups (.dbd.N--N.dbd.S),
nitramine groups (.dbd.N--NO.sub.2), thionitramine groups
(.dbd.N--NS.sub.2), carbonylnitrene groups (--CO--N),
thiocarbonylnitrene groups (--CS--N), sulfenyl halides (--S-X),
sulfoxides (.dbd.S.dbd.O), sulfones (.dbd.S[.dbd.O].sub.2),
sulfinyl groups (--N.dbd.S.dbd.O), thiosulfinyl groups
(--N.dbd.S.dbd.S), sulfenyl thiocyanato groups (--S--S--CN),
sulfenyl cyanato groups (--S--O--CN), sulfodiimine groups
(.dbd.S[.dbd.NH].sub.2), sulfur dihaloimido groups
(--N.dbd.SX.sub.2), sulfur oxide dihaloimido groups
(--N.dbd.S[.dbd.O]X.sub.2), aminosulfur oxide trihalide groups
(.dbd.N--S[.dbd.O]X.sub.3), sulfonyl azide groups
(--S[.dbd.O].sub.2N.sub.3), sulfonyl thiocyanate groups
(--S[.dbd.O].sub.2SCN), sulfonyl cyanate groups
(--S[.dbd.O].sub.2OCN), sulfonyl cyanide groups
(--S[.dbd.O].sub.2CN), halosulfonate groups (--S[.dbd.O].sub.2OX),
phosphonyl thiocyanate groups (--P[.dbd.O]OHSCN), phosphonyl
cyanate groups (--P[.dbd.O]OHOCN), and phosphonyl cyanide groups
(--P[.dbd.O]OHCN). The polarization of the Co.sup.+3-stabilizer can
therefore be optimized via evaluation of the effect of ligand type
and substituents. The influence of the Co.sup.+3 ion on the aqueous
solution outside of, or external to, the valence stabilizer shell
(or hydration sphere) may play an important role in the
complexation properties of a given ligand. It will also control the
diameter of the hydration shell around the Co.sup.+3-stabilizer
complex.
The number of binding sites available on the complexing ligand is
important to the resulting Co.sup.+3-stabilizer's properties.
Several ligands are required to stabilize Co.sup.+3 effectively if
the chosen ligand has only one binding site. Six NH.sub.3 ligands
are needed to octahedrally coordinate Co.sup.+3 in a
hexaaminecobalt(III) complex because NH.sub.3 has only one binding
site. Bulky ligands with only one binding site, like pyridine, can
be sterically hindered from packing tightly around the ion, which
will result in decreased complex stability. Conversely, macrocyclic
organic and polymeric inorganic ligands may have many suitable
binding sites. However, instability will result if a Co.sup.+3 ion
is not completely embraced by all of the multiple macromolecular
bonding sites on the ligand. For example, if a macromolecule
surrounding the Co.sup.+3 ion has an insufficient number of binding
sites available for charge balance, then the Co.sup.+3-stabilizer
complex will be much less stable than with a macromolecule that
contains an adequate number of sites.
The physical geometry of the binding sites is important to the
stability of the Co.sup.+3-stabilizer complex. The influence of
site geometry becomes evident when the solvation shell of a
Co.sup.+3 ion is replaced by the ligand donor atoms as when
conversion coatings are formed. The number of available ligand
binding sites should be at least equal to the standard coordination
number of the Co.sup.+3 ion. The balance between solvation of the
ligand and Co.sup.+3 and their complexation where Co.sup.+3 is
solvated by a specific ligand is critical in maintaining stability.
Co.sup.+3-ligand attraction increases with the number of available
binding sites on the ligand. However, with an increasing number of
binding sites, site-site repulsions will also increase, resulting
in lower stability.
The Co.sup.+3 ion generally favors complexation in the tetrahedral
(coordination number 4) or octahedral (coordination number 6)
arrangements. However, it will occasionally be found in a trigonal
bipyramidal or square planar arrangement. Valence stabilizers (and
stabilizer combinations) should be selected with the goal of
achieving these coordinations.
Inorganic materials that tend to "polymerize" and form octahedra or
tetrahedra (or a combination thereof) around ions such as Co.sup.+3
are termed isopolyanions, and their resultant complexes with
Co.sup.+3 are termed heteropolyanions or heteropolymetallates. This
polymerization of the inorganic valence stabilizer species results
in stacks of octahedra or tetrahedra with central cavities which
can accommodate at least one Co.sup.+3 ion, thereby stabilizing
it.
Valence stabilizers and combinations of stabilizers can be
manipulated by the selection of "shaping groups" and heteroatoms
positioned at the binding site. Inorganic valence stabilizers are
typically oxygen-containing coordination compounds. Saturated
organic chains can form flexible ligands that wrap around Co.sup.+3
and can enhance its stability. Unsaturated organics typically have
less freedom to bend and contort and are less likely to be able to
wrap around the Co.sup.+3 ion. The addition of substituents onto an
organic ligand may further restrict its freedom to flex.
The actual size of the valence stabilizer complex situated around
the Co.sup.+3 ion has an important role in solubility control.
Solubility of the complex scales roughly with the inverse of its
physical diameter. Co.sup.+3 and its layer of negatively charged
hydroxyl ions is very small and results in its high degree of
aqueous solubility. The field strength of the complex also scales
with the inverse of its physical diameter. Large complexes with an
optimal degree of solubility will not necessarily be ideal with
respect to the size of the electrostatic double layer. The size of
the ligand must, therefore, be balanced against the desired
electrical properties.
The addition (or subtraction) of functional groups on organic
valence stabilizers can be used to modify the solubility of the
formed Co.sup.+3/valence stabilizer species. For example, the
addition of sulfonated groups (--SO.sub.3.sup.-) to organic valence
stabilizers will significantly increase the solubility in water.
Other substituent groups that will increase the solubility in water
include: carboxyl groups (--CO.sub.2--), hydroxyl groups (--OH),
ester groups (--CO.sub.3.sup.-), carbonyl groups (.dbd.C.dbd.O),
amine groups (--NH.sub.2), nitrosamine groups (.dbd.N--N.dbd.O),
carbonylnitrene groups (--CO--N), sulfoxide groups (.dbd.S.dbd.O),
sulfone groups (.dbd.S[.dbd.O]2), sulfinyl groups
(--N.dbd.S.dbd.O), sulfodiimines (.dbd.S[.dbd.NH].sub.2), sulfonyl
halide groups (--S[.dbd.O].sub.2X), sulfonamide groups
(--S[.dbd.O].sub.2NH.sub.2), monohalosulfonamide groups
(--S[.dbd.O].sub.2NHX), dihalosulfonamide groups (--S
[.dbd.O].sub.2MX.sub.2), halosulfonate groups (--S
[.dbd.O].sub.2OX), halosulfonate amide groups
(.dbd.N--S[.dbd.O].sub.2X), aminosulfonate groups (.dbd.N--S[.dbd.O
].sub.2OH), iminodisulfonate groups (--N[SO.sub.3.sup.-].sub.2),
phosphonate groups (--PO.sub.3.sup.-2), phosphonamide groups
(--PO.sub.2NH.sub.2--), phosphondiamide groups
(--PO[NH.sub.2].sub.2), aminophosphonate groups
(.dbd.N--PO.sub.3.sup.-2), and iminodiphosphonate groups
(--N[PO.sub.3.sup.-2].sub.2). Conversely, the addition of nitro
groups (--NO.sub.2), perfluoroalkyl groups (--C.sub.xF.sub.2x+1),
perchloroalkyl groups (--C.sub.xCl.sub.2+1), nitramine groups
(.dbd.N--NO.sub.2), thioketone groups (.dbd.C.dbd.S), sulfenyl
halide groups (--S-X), or sulfur dihaloimide groups
(--N.dbd.SX.sub.2) to organic valence stabilizers will decrease the
solubility in water. In this way, the solubility characteristics of
valence stabilizers can be tailored to meet specific needs.
The physical, chemical, and electrostatic-requirements for the
design of effective Co.sup.+-stabilizer complexes results in lists
of stabilizers that may be divided into wide band or narrow band
stabilizer classes. The compounds listed here are general guides
for the initial selection of a coordination compound and do not
represent a complete or final list. New organic and inorganic
compounds are continuously being developed, compound toxicity
limits can change, and some currently available compounds may have
been overlooked. Tailoring substituent groups and the selection of
cations or anions for charge balance can influence whether a
particular Co.sup.+3-stabilizer complex will have a wide band or
narrow band character.
Valence stabilizers for trivalent cobalt that embody the desirable
characteristics of stabilizers as described above are typical when
designing a conversion coating for maximum effectiveness. These
"wide band" stabilizers result in the formation of compounds that
provide significant corrosion resistance when used with trivalent
cobalt. "Narrow band" valence stabilizers result in satisfactory
conversion coatings only under limited applications. Wide band
conversion coatings for general purpose applications and narrow
band conversion coatings for specific uses have been identified and
developed. In general, valence stabilizers that form cobalt
complexes which exhibit the necessary physical properties of
stability, solubility, and polarization may be achieved with both
inorganic and organic valence stabilizers. Ion exchange behavior
can also be achieved with both inorganic and organic coordination
compounds.
4a) Wide Band Inorganic Valence Stabilizers
Wide band inorganic stabilizers are formed around the Co.sup.+3 ion
by polymerizing in the conversion coating solution near the metal
surface being treated. Acidic coating solutions can become basic
near the metal surface where precipitation of the cobalt-stabilizer
complex occurs during the coating process. Inorganic wide band
valence stabilizers for Co.sup.+3 include, but are not limited to:
molybdates (Mo.sup.+6, Mo.sup.+5, or Mo.sup.+4, for example
[Co.sup.+3Mo.sub.6O.sub.18(OH).sub.6].sup.3-and
[Co.sup.+3.sub.2Mo.sub.10O.sub.34(OH).sub.4].sup.6-), tungstates
(W.sup.+6, W.sup.+5, or W.sup.+4, for example
[Co.sup.+3W.sub.12O.sub.40].sup.5-), vanadates (V.sup.+5 and
V.sup.+4, for example [Co.sup.+3V.sub.10O.sub.28].sup.3 -),
niobates (Nb.sup.+5 and Nb.sup.+4, for example
[Co.sup.+3Nb.sub.4O.sub.12(OH).sub.2].sup.3-), tantalates
(Ta.sup.+5 and Ta.sup.+4, for example
[Co.sup.+3Ta.sub.4O.sub.12(OH).sub.2].sup.3-), tellurates
(Te.sup.+6 and Te.sup.+4), periodates (I.sup.+7), iodates
(I.sup.+5, for example [Co.sup.+3(IO.sub.3).sub.4].sup.1 -),
carbonates (C.sup.+4, for example
[Co.sup.+3(CO.sub.3).sub.3].sup.3-), antimonates (Sb.sup.+5 and
Sb.sup.+3), and stannates (Sn.sup.+4). Many of these inorganics
form octahedral and tetrahedral heteropolymetallate structures on
precipitation from solution. For example, tellurate ions begin to
polymerize in solution near pH 5 and will complex with Co.sup.+3
ions near the metal substrate as solution pH increases. The exact
chemical nature of these valence stabilizers (i.e., chemical
formulation and valence state of the atom in the center of the
tetrahedra or octahedra) is highly dependent upon the specific pH
and redox conditions.
The stability of the heteropolymetallates is a function of
composition and structure. The relatively unstable Co.sup.+3 ion is
protected and stabilized within the surrounding octahedral and
tetrahedral groups, although specific configurations of the
heteropolymetallate anions differ from stabilizer to stabilizer
(i.e., from molybdate to periodate to carbonate).
The dimensions of the octahedra and tetrahedra are controlled by
the size of the heteroatom (e.g., Mo, W, Te) around which they are
assembled. A Co.sup.+3 ion trapped by the precipitation of these
heteropolymetallates and its resulting "ion within a cage"
structure can exhibit an even greater apparent volume due to the
development of a large electrostatic double layer. This will
influence both the valence stabilization of the Co.sup.+3 as well
as the solubility of the assembled complex. These compounds are
also reported to be excellent ion exchange agents for alkali
ions.
This caging structure serves to lower the solubility of the
Co.sup.+3 because the chemical elements typically associated with
these valence stabilizers (e.g., I, Te, Mo, W) are all inherently
less soluble in water than Co.sup.+3. These materials can also
establish oriented dipoles with the interior Co.sup.+3 ion, thereby
forming the desired barrier layers (e.g., of hydronium ions), much
as ferricyanide or molybdate probably contributes to the hexavalent
chrome systems. Finally, the elements associated with these valence
stabilizers themselves can contain high valence ions, such as
V.sup.+5, Te.sup.+6, or Mo.sup.+6, which will also serve somewhat
in corrosion protection, although not to the degree of Co.sup.+3,
due to their lower redox potential.
Water-soluble precursors for the formation of these valence
stabilizers are desirable in order to ensure that sufficient
material is available for coating deposition from aqueous
solutions. Identification of suitable water-soluble precursors may
be difficult, since many of the elements associated with these
valence stabilizers (e.g., Mo, W, Te, etc.) do not typically form
water-soluble compounds (hence their beneficial use as a valence
stabilizer). Representative examples of suitable precursors for
"wide band" inorganic valence stabilizers are listed in Table
6.
The solubilities given in Table 6 are usually for the simplest
salts of each compound. More complex, partially "polymerized" salts
for each compound (e.g., para- or meta-polymorphs) can also be used
as precursors, although these polymorphs typically exhibit slightly
lower solubilities in water than the simple salts. Peroxo-salts of
these compounds, especially percarbonates, permolybdates,
pertungstates, pertitanates, and pervanadates can also be utilized
as precursors. Formation of the chosen heteropolymetallates from
precursors such as the fluorides, chlorides, bromides, nitrates,
and perchlorates (e.g., SnCl.sub.4 to form heterostannates, and
SbF.sub.5 to form heteroantimonates) proved to be difficult, but
may be acceptable under certain circumstances.
Co.sup.+3 stabilized with a heteropolymolybdate complex is an
example of a wide band inorganically stabilized cobalt complex.
This complex is very stable and provides significant corrosion
protection when it is used as a conversion coating. The size of the
cavity developed at the center of a ligand with three or more
bonding sites is important. A cavity that is too large or too small
will tend to be less stable and less effective in use as a
corrosion inhibitor.
The valence stabilizer can be a cross between two or more of the
wide-band inorganic valence stabilizers listed above. For example,
in some instances it may be desirable to form a valence stabilizer
out of a periodate and a molybdate. During the coating process,
both of these materials will polymerize to form a mixed
periodate/molybdate valence stabilizer out of the conversion
coating solution.
4b) Wide Band Organic Valence Stabilizers
A variety of organic compounds meet the criteria to be typical
valence stabilizers for Co.sup.+3. These coordination ligands
produce Co.sup.+3 valence stabilized complexes which fulfill the
general requirements of a Co.sup.+3 conversion coating material.
Organic compounds can be very effective cobalt stabilizers and
provide the greatest degree of freedom in designing new stabilizer
species with new functionalities. There are many more possible
organic valence stabilizer species than inorganic valence
stabilizers because of the large number of organic compounds and
functionalities which exist. Some of the typical organic valence
stabilizer species are listed in Table 1 below.
The number of wide band (and narrow band) organic compounds that
are acceptable as valence stabilizers for trivalent cobalt is
limited. Common organic compounds such as alcohols, aldehydes,
ketones, esters, ethers, alkyl or aromatic halides, most carboxylic
acids, anhydrides, phenols, sulfonic acids, phosphonic acids,
carbohydrates, waxes, fats, sugars, and oils are not as effective
as the structural types described in these Tables to stabilize the
trivalent cobalt ion. At best, some of the organic types described
in these Tables may presently be used for other industrial
applications, but their incorporation into corrosion-inhibiting
blends to stabilize trivalent cobalt has heretofore been
unrecognized.
The choice of substituent functional groups on these general
classes of valence stabilizers will affect the physicochemical
properties of the Co.sup.+3-containing complex and the corrosion
resistance achieved using that complex. For example, the addition
of --NH.sub.2, or 0 substituents increases the net polarization of
the overall Co.sup.+3-valence stabilizer complex, but this will
also increase its water solubility. Careful molecular design of
Co.sup.+3 complexes is necessary to achieve desired performance
characteristics.
In general, the bonding atoms in typical organic valence
stabilizers are nitrogen, phosphorus, or sulfur, with oxygen being
acceptable in some circumstances. Oxygen is complexed with
Co.sup.+3 most frequently in association with at least one of the
other three. Bonding atoms such as carbon, silicon, tin, arsenic,
selenium, and antimony are much less desirable due to problems with
valence stability, toxicity, or solubility. Other stable
coordinations (like octahedral) are known, even though these
particular agents are shown in tetrahedral coordination with
Co.sup.+3. These valence stabilizers all serve to stabilize the
Co.sup.+3 ion within a sparingly soluble complex that can exhibit a
polar character in aqueous solution.
TABLE-US-00002 TABLE 1 Wide Band Organic Valence Stabilizers for
the Co.sup.+3 Ion General Structural Name (Type of Organic)
Structural Representation N Valence Stabilizer #1: NH.sub.3,
NH.sub.2R, NHR.sub.2, and NR.sub.3 where R Monoamines (N
Monodentates) represents H or any organic functional group wherein
the number of carbon atoms ranges from 0 to 40, optionally having
halogen or polarizing or water-insolubilizing/solubilizing groups
attached. Ligand can also contain nonbinding N, O, S, or P atoms. N
Valence Stabilizer #2: R'--N--R--N--R'', where R, R', and R''
represent H Diamines (N--N Bidentates) or any organic functional
group wherein the number of carbon atoms ranges from 0 to 40,
optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N Valence Stabilizer #3:
R--N--R'--N--R''--N--R''', where R, R', R'', and R''' Triamines
(either N--N Bidentates or N--N represent H or any organic
functional group Tridentates) wherein the number of carbon atoms
ranges from 0 to 40, optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N Valence Stabilizer #4:
R--N--R'--N--R''--N--R'''--N--R'''', where R, R', R'', Tetramines
(N--N Bidentates, N--N R''', and R'''' represent H or any organic
Tridentates, or N--N Tetradentates) functional group wherein the
number of carbon atoms ranges from 0 to 40, optionally having
halogen or polarizing or water- insolubilizing/solubilizing groups
attached. Ligand can also contain nonbinding N, O, S, or P atoms. N
Valence Stabilizer #5:
R--N--R'--N--R''--N--R'''--N--R''''--N--R''''', where R, Pentamines
(N--N Bidentates, N--N R', R'', R''', R'''', and R''''' represent H
or any Tridentates, or N--N Tetradentates) organic functional group
wherein the number of carbon atoms ranges from 0 to 40, optionally
having halogen or polarizing or water- insolubilizing/solubilizing
groups attached. Ligand can also contain nonbinding N, O, S, or P
atoms. N Valence Stabilizer #6:
R--N--R'--N--R''--N--R'''--N--R''''--N--R'''''--N--R'''''',
Hexamines (N--N Bidentates, N--N where R, R', R'', R''', R'''',
R''''', and R'''''' Tridentates, N--N Tetradentates, or N--N
represent H or any organic functional group Hexadentates) wherein
the number of carbon atoms ranges from 0 to 40, optionally having
halogen or polarizing or water-insolubilizing/solubilizing groups
attached. Ligand can also contain nonbinding N, O, S, or P atoms. N
Valence Stabilizer #7: Five membered heterocyclic ring containing
Five-Membered Heterocyclic Rings one, two, three, or four nitrogen
atoms, all of containing One, Two, Three, or Four which may or may
not function as binding sites. Nitrogen Atoms wherein at least one
Can include other ring systems bound to this Nitrogen Atom is a
Binding Site (N heterocyclic ring, but they do not coordinate
Monodentates or N--N Bidentates) with the stabilized, high valence
metal ion. Ring can also contain O, S, or P atoms. This 5- membered
ring and/or attached, uncoordinating rings may or may not have
halogen or polarizing or water-insolubilizing/solubilizing groups
attached. N Valence Stabilizer #8: Six membered heterocyclic ring
containing one, Six-Membered Heterocyclic Rings two, three, or four
nitrogen atoms, all of which containing One, Two, Three, or Four
may or may not function as binding sites. Can Nitrogen Atoms
wherein at least one include other ring systems bound to this
Nitrogen Atom is a Binding Site (N heterocyclic ring, but they do
not coordinate Monodentates or N--N Bidentates) with the
stabilized, high valence metal ion. Ring can also contain O, S, or
P atoms. This 6- membered ring and/or attached, uncoordinating
rings may or may not have halogen or polarizing or
water-insolubilizing/solubilizing groups attached. N Valence
Stabilizer #9: Five membered heterocyclic ring(s) containing
Five-Membered Heterocyclic Rings one, two, three, or four nitrogen
atoms. In containing One, Two, Three, or Four addition, ligand
contains additional nitrogen- Nitrogen Atoms and having at least
one containing substituents (usually amines) that additional
Nitrogen Atom Binding Site not constitute N binding sites. Can
include other in a Ring (N Monodentates, N--N ring systems bound to
the heterocyclic ring or to Bidentates, N Tridentates, N--N the
N-containing substiruent, but they do not Tetradentates, or N--N
Hexadentates) coordinate with the stabilized, high valence metal
ion. Ring(s) can also contain O, S, or P atoms. This 5-membered
ring(s) and/or attached, uncoordinating rings and/or N- containing
substituent(s) may or may not have halogen or polarizing or water-
insolubilizing/solubilizing groups attached. N Valence Stabilizer
#10: Six membered heterocyclic ring(s) containing Six-Membered
Heterocyclic Rings one, two, three, or four nitrogen atoms. In
containing One, Two, Three, or Four addition, ligand contains
additional nitrogen- Nitrogen Atoms at least one additional
containing substituents (usually amines) that Nitrogen Atom Binding
Site not in a Ring constitute N binding sites. Can include other (N
Monodentates, N--N Bidentates, N--N ring systems bound to the
heterocyclic ring or to Tridentates, N--N Tetradentates, or N--N
the N-containing substituent, but they do not Hexadentates)
coordinate with the stabilized, high valence metal ion. Ring(s) can
also contain O, S, or P atoms. This 6-membered ring(s) and/or
attached, uncoordinating rings and/or N- containing substituent(s)
may or may not have halogen or polarizing or water-
insolubilizing/solubilizing groups attached. N Valence Stabilizer
#11: Five membered heterocyclic ring(s) containing Five-Membered
Heterocyclic Rings one, two, three, or four nitrogen atoms. In
containing One, Two, Three, or Four addition, ligand contains
additional nitrogen- Nitrogen Atoms at least one additional
containing rings that constitute N binding sites. Nitrogen Atom
Binding Site in a Separate Can include other ring systems bound to
the N- Ring (N Monodentates, N--N Bidentates, N-- containing
heterocyclic rings, but they do not N Tridentates, N--N
Tetradentates) coordinate with the stabilized, high valence metal
ion. Ring(s) can also contain O, S, or P atoms. This 5-membered
ring(s) and/or additional N-containing ring(s) and/or attached,
uncoordinating rings may or may not have halogen or polarizing or
water- insolubilizing/solubilizing groups attached. N Valence
Stabilizer #12: Six membered heterocyclic ring(s) containing
Six-Membered Heterocyclic Rings one, two, three, or four nitrogen
atoms. In containing One, Two, Three, or Four addition, ligand
contains additional nitrogen- Nitrogen Atoms at least one
additional containing rings that constitute N binding sites.
Nitrogen Atom Binding Site in a Separate Can include other ring
systems bound to the N- Ring (N Monodentates, N--N Bidentates, N--
containing heterocyclic rings, but they do not N Tridentates, N--N
Tetradentates) coordinate with the stabilized, high valence metal
ion. Ring(s) can also contain O, S, or P atoms. This 6-membered
ring(s) and/or additional N-containing ring(s) and/or attached,
uncoordinating rings may or may not have halogen or polarizing or
water- insolubilizing/solubilizing groups attached. N Valence
Stabilizer #13: Macrocyclic ligands containing two, three, four,
Two-, Three-, Four-, Six-, Eight-, and Ten- six, eight, or ten
nitrogen binding sites to Membered Macrocyclics, Macrobicyclics,
valence stabilize the central metal ion. Can and Macropolycyclics
(including include other hydrocarbon or ring systems Catapinands,
Cryptands, Cyclidenes, and bound to this macrocyclic ligand, but
they do Sepulchrates) wherein all Binding Sites are not coordinate
with the stabilized, high valence composed of Nitrogen (usually
amine or metal ion. This ligand and/or attached, imine groups) and
are not contained in uncoordinating hydrocarbons/rings may or may
Component Heterocyclic Rings (N--N not have halogen or polarizing
or water- Bidentates, N--N Tridentates, N--N
insolubilizing/solubilizing groups attached. Tetradentates, and
N--N Hexadentates) N Valence Stabilizer #14: Macrocyclic ligands
containing a total of four, Four-, Six-, Eight-, or Ten-Membered
six, eight, or ten five-membered heterocyclic Macrocyclics,
Macrobicyclics, and rings containing nitrogen binding sites. Can
Macropolycyclics (including Catapinands, include other
hydrocarbon/ring systems bound Cryptands, Cyclidenes, and
Sepulchrates) to this macrocyclic ligand, but they do not wherein
all Binding Sites are composed of coordinate with the stabilized,
high valence Nitrogen and are contained in Component metal ion.
This ligand and/or attached, 5-Membered Heterocyclic Rings (N--N
uncoordinating hydrocarbon/rings may or may Bidentates, N--N
Tridentates, N--N not have halogen or polarizing or water-
Tetradentates, or N--N Hexadentates) insolubilizing groups
attached. N Valence Stabilizer #15: Macrocyclic ligands containing
at least one 5- Four-, Six-, Eight-, or Ten-Membered membered
heterocyclic ring. These Macrocyclics, Macrobicyclics, and
heterocyclic rings provide nitrogen binding sites Macropolycyclics
(including Catapinands, to valence stabilize the central metal ion.
Other Cryptands, Cyclidenes, and Sepulchrates) amine or imine
binding sites can also be wherein all Binding Sites are composed of
included in the macrocyclic ligand, so long as Nitrogen and are
contained in a the total number of binding sites is four, six,
Combination of 5-Membered Heterocyclic eight, or ten. Can include
other Rings and Amine or Imine Groups (N--N hydrocarbon/ring
systems bound to this Bidentates, N--N Tridentates, N--N
macrocyclic ligand, but they do not coordinate Tetradentates, or
N--N Hexadentates) with the stabilized, high valence metal ion.
This ligand and/or attached, uncoordinating hydrocarbon/rings may
or may not have halogen or polarizing or water-insolubilizing
groups attached. N Valence Stabilizer #16: Macrocyclic ligands
containing a total of four, Four-, Six-, Eight-, or Ten-Membered
six, eight, or ten six-membered heterocyclic Macrocyclics,
Macrobicyclics, and rings containing nitrogen binding sites. Can
Macropolycyclics (including Catapinands, include other
hydrocarbon/ring systems bound Cryptands, Cyclidenes, and
Sepulchrates) to this macrocyclic ligand, but they do not wherein
all Binding Sites are composed of coordinate with the stabilized,
high valence Nitrogen and are contained in Component metal ion.
This ligand and/or attached, 6-Membered Heterocyclic Rings (N--N
uncoordinating hydrocarbon/rings may
or may Bidentates, N--N Tridentates, N--N not have halogen or
polarizing or water- Tetradentates, or N--N Hexadentates)
insolubilizing groups attached. N Valence Stabilizer #17:
Macrocyclic ligands containing at least one 6- Four-, Six-, Eight-,
or Ten-Membered membered heterocyclic ring. These Macrocyclics,
Macrobicyclics, and heterocyclic rings provide nitrogen binding
sites Macropolycyclics (including Catapinands, to valence stabilize
the central metal ion. Other Cryptands, Cyclidenes, and
Sepulchrates) amine or imine binding sites can also be wherein all
Binding Sites are composed of included in the macrocyclic ligand,
so long as Nitrogen and are contained in a the total number of
binding sites is four, six, Combination of 6-Membered Heterocyclic
eight, or ten. Can include other Rings and Amine or Imine Groups
(N--N hydrocarbon/ring systems bound to this Bidentates, N--N
Tridentates, N--N macrocyclic ligand, but they do not coordinate
Tetradentates, or N--N Hexadentates) with the stabilized, high
valence metal ion. This ligand and/or attached, uncoordinating
hydrocarbon/rings may or may not have halogen or polarizing or
water-insolubilizing groups attached. N Valence Stabilizer #18:
R'--NH--C(--R).dbd.N--R'', where R, R', and R'' Amidines and
Diamidines (N--N Bidentates represent H or any organic functional
group and N--N Tetradentates) wherein the number of carbon atoms
ranges from 0 to 40, optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N Valence Stabilizer #19:
RR'--N--C(.dbd.NH)--NR''--C(.dbd.NH)--NR'''R'''' for Biguanides
(Imidodicarbonimidic Diamides biguanides,
RR'--N--C(.dbd.NH)--NR''--NH--C(.dbd.NH)-- or Dihydrazides),
Biguanidines, NR'''R'''' for biguanidines, where R, R', R'',
Imidotricarbonimidic Diamides or R''', and R'''' represent H,
NH.sub.2, or any organic Dihydrazides, Imidotetracarbonimidic
functional group wherein the number of carbon Diamides or
Dihydrazides, Dibiguanides, atoms ranges from 0 to 40, halogen or
Bis(biguanidines), Polybiguanides, and polarizing or
water-insolubilizing/solubilizing Poly(biguanidines) (N--N
Bidentates, N--N groups attached. Ligand can also contain
Tridentates, N--N Tetradentates, and N--N nonbinding N, O, S, or P
atoms. Hexadentates) N Valence Stabilizer #20:
RR'--N--C(.dbd.NH)--CR''R'''--C(.dbd.NH)--NR''''R''''',
Diamidinomethanes, where R, R', R'', R''', R'''', and R'''''
represent Bis(amidinomethanes), and H, NH.sub.2, or any organic
functional group Poly(amidinomethanes) (N--N Bidentates, wherein
the number of carbon atoms ranges N--N Tridentates, N--N
Tetradentates, and N-- from 0 to 40, optionally having halogen or N
Hexadentates) polarizing or water-insolubilizing/solubilizing
groups attached. Ligand can also contain nonbinding N, O, S, or P
atoms. N Valence Stabilizer #21:
RR'--N--C(.dbd.NH)--NR''--C(.dbd.NH)--R''' for Imidoylguanidines,
Amidinoguanidines, imidoylguanidines, and
RR'--N--C(.dbd.NH)--NR''-- Bis(imidoylguanidines),
NH--C(.dbd.NH)--R''' for amidinoguanidines, where
Bis(amidinoguanidines), R, R', R'', and R''' represent H, NH.sub.2,
or any Poly(imidoylguanidines), and organic functional group
wherein the number of Poly(amidinoguanidines) (N--N Bidentates,
carbon atoms ranges from 0 to 40, optionally N--N Tridentates, N--N
Tetradentates) having halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N Valence Stabilizer #22:
RR'--N--C(.dbd.NH)--O--C(.dbd.NH)--NR''R''', where R, Diformamidine
oxides (Dicarbonimidic R', R'', and R''' represent H, NH.sub.2, or
any Diamides or Dihydrazides), organic functional group wherein the
number of Tricarbonimidic Diamides or Dihydrazides, carbon atoms
ranges from 0 to 40, optionally Tetracarbonimidic Diamides or
having halogen or polarizing or water- Dihydrazides,
Bis(diformamidine oxides), insolubilizing/solubilizing groups
attached. and Poly(diformamidine oxides) (N--N Ligand can also
contain nonbinding N, O, S, or Bidentates, N--N Tridentates, N--N P
atoms. Tetradentates) N Valence Stabilizer #23:
RR'--N--C(.dbd.NH)--S--C(.dbd.NH)--NR''R''', where R, Diformamidine
Sulfides R', R'', and R''' represent H, NH.sub.2, or any
(Thiodicarbonimidic Diamides or organic functional group wherein
the number of Dihydrazides), Thiotricarbonimidic carbon atoms
ranges from 0 to 40, optionally Diamides or Dihydrazides, having
halogen or polarizing or water- Thiotetracarbonimidic Diamides or
insolubilizing/solubilizing groups attached. Dihydrazides,
Bis(diformamidine sulfides), Ligand can also contain nonbinding N,
O, S, or and Poly(diformamidine sulfides) (N--N P atoms.
Bidentates, N--N Tridentates, N--N Tetradentates) N Valence
Stabilizer #24: R--O--C(.dbd.NH)--NR'--C(.dbd.NH)--O--R'' for
Imidodicarbonimidic Acids, imidodicarbomimidic acids, and
R--O--C(.dbd.NH)-- Diimidodicarbonimidic Acids,
NR'--NH--C(.dbd.NH)--O--R'' for Imidotricarbonimidic Acids,
diimidodicarbonimidic acids, where R, R', and
Imidotetracarbonimidic Acids, and R'' represent H, NH.sub.2, or any
organic functional derivatives thereof (N--N Bidentates, N--N group
wherein the number of carbon atoms Tridentates, N--N Tetradentates,
and N--N ranges from 0 to 40, optionally having halogen
Hexadentates) or polarizing or water- insolubilizing/solubilizing
groups attached. Ligand can also contain nonbinding N, O, S, or P
atoms. N Valence Stabilizer #25:
R--S--C(.dbd.NH)--NR'--C(.dbd.NH)--S--R'' for
Thioimidodicarbonimidic Acids, thioimidodicarbonimidic acids, and
R--S-- Thiodiimidodicarbonimidic Acids,
C(.dbd.NH)--NR'--NH--C(.dbd.NH)--S--R'' for
Thioimidotricarbonimidic Acids, thiodiimidodicarbonimidic acids,
where R, R', Thioimidotetracarbonimidic Acids, and and R''
represent H, NH.sub.2, or any organic derivatives thereof (N--N
Bidentates, N--N functional group wherein the number of carbon
Tridentates, N--N Tetradentates, and N--N atoms ranges from 0 to
40, optionally having Hexadentates) halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N Valence Stabilizer #26:
Diimidoylimines, R--C(.dbd.NH)--NR'--C(.dbd.NH)--R'' for
Diimidoylhydrazides, diimidoylimines, and R--C(.dbd.NH)--NR'--NH--
Bis(diimidoylimines), C(.dbd.NH)--R'' for diimidoylhydrazides,
where R, Bis(diimidoylhydrazides), R', and R'' represent H,
NH.sub.2, or any organic Poly(diimidoylimines), and functional
group wherein the number of carbon Poly(diimidoylhydrazides) (N--N
atoms ranges from 0 to 40, optionally having Tridentates and N--N
Hexadentates) halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N Valence Stabilizer #27:
RR'--N--S(.dbd.NH)(.dbd.O)--OR'' or RR'--N-- Imidosulfamides,
Diimidosulfamides, S(.dbd.NH)(.dbd.O)--N--R''R''' for
imidosulfamides, and Bis(imidosulfamides),
RR'--N--S(.dbd.NH)(.dbd.NH)--OR'' or RR'--N--
Bis(diimidosulfamides), S(.dbd.NH)(.dbd.NH)--N--R''R''' for
diimidosulfamides, Poly(imidosulfamides), and where R, R', R'', and
R''' represent H, NH.sub.2, or Poly(diimidosulfamides) (N--N
Bidentates, any organic functional group wherein the N--N
Tridentates, N--N Tetradentates, and N-- number of carbon atoms
ranges from 0 to 40, N Hexadentates) optionally having halogen or
polarizing or water-insolubilizing/solubilizing groups attached.
Ligand can also contain nonbinding N, O, S, or P atoms. N Valence
Stabilizer #28: (NH.dbd.)P(--NRR')(--NR''R''')(--NR''''R'''''),
where Phosphoramidimidic Triamides, R, R', R'', R''', R'''', and
R''''' represent H, NH.sub.2, Bis(phosphoramidimidic triamides),
and or any organic functional group wherein the
Poly(phosphoramidimidic triamides) and number of carbon atoms
ranges from 0 to 40, derivatives thereof (N--N Bidentates, N--N
optionally having halogen or polarizing or Tridentates, N--N
Tetradentates, and N--N water-insolubilizing/solubilizing groups
Hexadentates) attached. Ligand can also contain nonbinding N, O, S,
or P atoms. N Valence Stabilizer #29: (NH.dbd.)P(--NRR')(OH).sub.2
for phosphoramidimidic Phosphoramidimidic Acid, acid, and
(NH.dbd.)P(--NRR')(--NR''R''')(OH) for Phosphorodiamidimidic Acid,
phosphorodiamidimidic acid, where R, R', R'',
Bis(Phosphoramidimidic Acid), and R''' represent H, NH.sub.2, or
any organic Bis(Phosphorodiamidimidic Acid), functional group
wherein the number of carbon Poly(Phosphoramidimidic Acid), atoms
ranges from 0 to 40, optionally having Poly(Phosphorodiamidimidic
Acid), and halogen or polarizing or water- derivatives thereof
(N--N Bidentates, N--N insolubilizing/solubilizing groups attached.
Tridentates, N--N Tetradentates, and N--N Ligand can also contain
nonbinding N, O, S, or Hexadentates) P atoms. N Valence Stabilizer
#30: (NH.dbd.)P(--NRR')(SH).sub.2 for Phosphoramidimidodithioic
Acid, phosphoramidimidodithioic acid, and (NH.dbd.)P(--
Phosphorodiamidimidothioic Acid, NRR')(--NR''R''')(SH) for
Bis(Phosphoramidimidodithioic Acid), phosphorodiamidimidothioic
acid, where R, R', Bis(Phosphorodiamidimidothioic Acid), R'', and
R''' represent H, NH.sub.2, or any organic
Poly(Phosphoramidimidodithioic Acid), functional group wherein the
number of carbon Poly(Phosphorodiamidimidothioic Acid), atoms
ranges from 0 to 40, optionally having and derivatives thereof
(N--N Bidentates, N-- halogen or polarizing or water- N
Tridentates, N--N Tetradentates, and N--N
insolubilizing/solubilizing groups attached. Hexadentates) Ligand
can also contain nonbinding N, O, S, or P atoms. N Valence
Stabilizer #31: R--N.dbd.N--R', where R, and R' represent H or any
Azo compounds with amino, imino, oximo, organic functional group
wherein the number of diazeno, or hydrazido substitution at the
carbon atoms ranges from 0 to 40, optionally ortho- (for aryl) or
alpha- or beta- (for having halogen or polarizing or water- alkyl)
positions, Bis[o-(H.sub.2N--) or alpha- or
insolubilizing/solubilizing groups attached. beta-(H.sub.2N--)azo
compounds], or Poly[o- (Must include ortho-amino, imino, oximo,
(H.sub.2N--) or alpha- or beta-(H.sub.2N--)azo diazeno, or
hydrazido substituted aryl azo compounds) (N--N Bidentates, N--N
compounds, and alpha- or beta-amino, imino, Tridentates, N--N
Tetradentates, or N--N oximo, diazeno, or hydrazido alkyl azo
Hexadentates) compounds.) Ligand can also contain nonbinding N, O,
S, or P atoms. N Valence Stabilizer #32:
R--N.dbd.N--C(.dbd.NH)--NR'R'' for Diazeneformimidamides
diazeneformimidamides, and R--N.dbd.N--CR'R''-- (Diazeneamidines),
Diazeneacetimidamides C(.dbd.NH)--NR'''R'''' for
diazeneacetimidamides, (Diazene-alpha-amidinoalkanes(alkenes)),
where R, R', R'', R''', and R'''' represent H,
Bis(diazeneformimidamides), NH.sub.2, or any organic functional
group wherein Bis(diazeneacetimidamides), the number of carbon
atoms ranges from 0 to Poly(diazeneformimidamides), and 40,
optionally having halogen or polarizing or
Poly(diazeneacetimidamides) (N--N water-insolubilizing/solubilizing
groups Bidentates, N--N Tetradentates, and N--N attached. Ligand
can also contain nonbinding
Hexadentates) N, O, S, or P atoms. N Valence Stabilizer #33:
R--N.dbd.N--C(.dbd.NH)--OR' for diazeneformimidic Diazeneformimidic
Acid, acid, and R--N.dbd.N--CR'R''--C(.dbd.NH)--OR''' for
Diazeneacetimidic Acid, diazeneacetimidic acid, where R, R', R'',
and Bis(diazeneformimidic acid), R''' represent H, NH.sub.2, or any
organic functional Bis(diazeneacetimidic acid), group wherein the
number of carbon atoms Poly(diazeneformimidic acid), ranges from 0
to 40, optionally having halogen Poly(diazeneacetimidic acid), and
or polarizing or water- derivatives thereof (N--N Bidentates, N--N
insolubilizing/solubilizing groups attached. Tetradentates, and
N--N Hexadentates) Ligand can also contain nonbinding N, O, S, or P
atoms. N Valence Stabilizer #34: R--N.dbd.N--C(.dbd.NH)--SR' for
Diazeneformimidothioic Acid, diazeneformimidothioic acid, and
R--N.dbd.N-- Diazeneacetimidothioic Acid, CR'R''--C(.dbd.NH)--SR'''
for Bis(diazeneformimidothioic acid), diazeneacetimidothioic acid,
where R, R', R'', Bis(diazeneacetimidothioic acid), and R'''
represent H, NH.sub.2, or any organic Poly(diazeneformimidothioic
acid), functional group wherein the number of carbon
Poly(diazeneacetimidothioic acid), and atoms ranges from 0 to 40,
optionally having derivatives thereof (N--N Bidentates, N--N
halogen or polarizing or water- Tetradentates, and N--N
Hexadentates) insolubilizing/sohibilizing groups attached. Ligand
can also contain nonbinding N, O, S, or P atoms. N Valence
Stabilizer #35: R--N.dbd.N--C(.dbd.NH)--R' or R--N.dbd.N--CR'R''--
Imidoyldiazenes, Bis(imidoyldiazenes), and C(.dbd.NH)--R''', where
R, R', R'', and R''' Poly(imidoyldiazenes), (N--N Bidentates, N--
represent H, NH.sub.2, or any organic functional N Tetradentates
and N--N Hexadentates) group wherein the number of carbon atoms
ranges from 0 to 40, optionally having halogen or polarizing or
water- insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N Valence Stabilizer #36:
RR'--N--C(.dbd.NH)--N.dbd.N--C(.dbd.NH)--NR''R'''for
Diazenediformimidamides (1,2- diazenediformimidamides, and
RR'--N--C(.dbd.NH)-- Diazenediamidines),
CR''R'''--N.dbd.N--CR''''R'''''--C(.dbd.NH)--NR''''''R- '''''''
Diazenediacetimidamides (1,2-Diazene-di- for
diazenediacetimidamides, where R, R', R'',
alpha-amidinoalkanes(alkenes)), R''', R'''', R''''', R'''''', and
R''''''' represent H, Bis(diazenediformimidamides), NH.sub.2, or
any organic functional group wherein Bis(diazenediacetimidamides),
the number of carbon atoms ranges from 0 to
Poly(diazenediformimidamides), and 40, optionally having halogen or
polarizing or Poly(diazenediacetimidamides) (N--N
water-insolubilizing/solubilizing groups Tridentates and N--N
Hexadentates) attached. Ligand can also contain nonbinding N, O, S,
or P atoms. N Valence Stabilizer #37:
RO--C(.dbd.NH)--N.dbd.N--C(.dbd.NH)--OR' for Diazenediformimidic
Acid, diazenediformimidic acid, and RO--C(.dbd.NH)--
Diazenediacetimidic Acid,
CR'R''--N.dbd.N--CR'''R''''--C(.dbd.NH)--OR''''' for
Bis(diazenediformimidic acid), diazenediacetimidic acid, where R,
R', R'', R''', Bis(diazenediacetimidic acid), R'''', and R'''''
represent H, NH.sub.2, or any organic Poly(diazenediformimidic
acid), and functional group wherein the number of carbon
Poly(diazenediacetimidic acid), and atoms ranges from 0 to 40,
optionally having derivatives thereof (N--N Tridentates and N--
halogen or polarizing or water- N Hexadentates)
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N Valence Stabilizer #38:
RS--C(.dbd.NH)--N.dbd.N--C(.dbd.NH)--SR' for
Diazenediformimidothioic Acid, diazenediformimidothioic acid, and
RS-- Diazenediacetimidothioic Acid,
C(.dbd.NH)--CR'R''--N.dbd.N--CR'''R''''--C(.dbd.NH)--SR'''''
Bis(diazenediformimidothioic acid), for diazenediacetimidothioic
acid, where R, R', Bis(diazenediacetimidothioicacid), R'', R''',
R'''', and R''''' represent H, NH.sub.2, or any
Poly(diazenediformimidothioic acid), and organic functional group
wherein the number of Poly(diazenediacetimidothioic acid), and
carbon atoms ranges from 0 to 40, optionally derivatives thereof
(N--N Tridentates and N-- having halogen or polarizing or water- N
Hexadentates) insolubilizing/solubilizing groups attached. Ligand
can also contain nonbinding N, O, S, or P atoms. N Valence
Stabilizer #39: R--C(.dbd.NH)--N.dbd.N--C(.dbd.NH)--R'' or
R--C(.dbd.NH)-- Diimidoyldiazenes, Bis(diimidoyldiazenes),
CR'R''--N.dbd.N--CR'''R''''--C(.dbd.NH)--R''''', where R, and
Poly(diimidoyldiazenes), (N--N R', R'', R''', R'''', and R'''''
represent H, NH.sub.2, or Tridentates and N--N Hexadentates) any
organic functional group wherein the number of carbon atoms ranges
from 0 to 40, optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N Valence Stabilizer #40:
R--N.dbd.N--CR'.dbd.N--NR''R''', where R, R', R'', and Ortho-amino
(or -hydrazido) Substituted R''' represent H, or any organic
functional Formazans, Bis(o-amino or -hydrazido group wherein the
number of carbon atoms substituted formazans), and Poly(o-amino
ranges from 0 to 40, optionally having halogen or -hydrazido
substituted formazans) (N--N or polarizing or water- Bidentates,
N--N Tridentates, N--N insolubilizing/solubilizing groups attached.
Tetradentates, and N--N Hexadentates) (Must include ortho-amine or
hydrazide substituted aryl R derivatives, and beta-amine or
hydrazide substituted alkyl R derivatives.) Ligand can also contain
nonbinding N, O, S, or P atoms. N Valence Stabilizer #41:
RR'C.dbd.N--N.dbd.CR''R''' or RR'C.dbd.N--NR''R''' (for Ortho-amino
(or -hydrazido) Substituted ketazines), where R, R', R'', and R'''
represent Azines (including ketazines), Bis(o-amino H, or any
organic functional group wherein the or hydrazido substituted
azines), and number of carbon atoms ranges from 0 to 40,
Poly(o-amino or hydrazido substituted optionally having halogen or
polarizing or azines) (N--N Bidentates, N--N Tridentates,
water-insolubilizing/solubilizing groups N--N Tetradentates, and
N--N Hexadentates) attached. (Must include ortho-amine or hydrazide
substituted aryl R derivatives, and beta-amine or hydrazide
substituted alkyl R derivatives.) Ligand can also contain
nonbinding N, O, S, or P atoms. N Valence Stabilizer #42:
RR'C.dbd.N--R'', where R, R', and R'' represent H, Schiff Bases
with one Imine (C.dbd.N) Group or any organic functional group
wherein the and with ortho- or alpha- or beta-amino or number of
carbon atoms ranges from 0 to 40, imino or oximo or diazeno or
hydrazido optionally having halogen or polarizing or substitution
(N--N Bidentates, N--N water-insolubilizing/solubilizing groups
Tridentates, N--N Tetradentates, N--N attached. (Must contain
ortho- or alpha- or Pentadentates, or N--N Hexadentates). Also
beta-amino or imino or oximo or diazeno or includes hydrazones with
ortho--N hydrazido substitution.) Ligand can also substitution.
contain nonbinding N, O, S, or P atoms. N Valence Stabilizer #43:
RR'C.dbd.N--R''--N.dbd.CR'''R'''' or R--N.dbd.C--R'--C.dbd.N--
Schiff Bases with two Imine (C.dbd.N) Groups R' or
RC.dbd.N--R'--N.dbd.CR'', where R, R', R'', R''', and without
ortho- (for aryl constituents) or and R'''' represent H, or any
organic functional alpha- or beta- (for alkyl constituents) group
wherein the number of carbon atoms hydroxy, carboxy, carbonyl,
thiol, ranges from 0 to 40, optionally having halogen mercapto,
thiocarbonyl, amino, imino, or polarizing or water- oximo, diazeno,
or hydrazido substitution insolubilizing/solubilizing groups
attached. (Not (N--N Bidentates). Also includes including ortho-,
alpha-, or beta-hydroxy, dihydrazones. carboxy, carbonyl, thiol,
mercapto, thiocarbonyl, amino, imino, oximo, diazeno, or hydrazido
substitution.) Ligand can also contain nonbinding N, O, S, or P
atoms. N Valence Stabilizer #44: RR'C.dbd.N--R''--N.dbd.CR'''R''''
or R--N.dbd.C--R'--C.dbd.N-- Schiff Bases with two Imine (C.dbd.N)
Groups R' or RC.dbd.N--R'--N.dbd.CR'', where R, R', R'', R''', and
with ortho- or alpha- or beta-amino or and R'''' represent H, or
any organic functional imino or oximo or diazeno or hydrazido group
wherein the number of carbon atoms substitution (N--N Tridentates,
N--N ranges from 0 to 40, optionally having halogen Tetradentates,
N--N Pentadentates, or N--N or polarizing or water- Hexadentates).
Also includes hydrazones insolubilizmg/solubilizing groups
attached. with ortho-N substitution. (Must contain ortho- or alpha-
or beta-amino or imino or oximo or diazeno or hydrazido
substitution.) Ligand can also contain nonbinding N, O, S, or P
atoms. N Valence Stabilizer #45: N(--R--N.dbd.CR'R'').sub.3, where
R, R', and R'' Schiff Bases with three Imine (C.dbd.N) represent H,
or any organic functional group Groups and without ortho- (for aryl
wherein the number of carbon atoms ranges constituents) or alpha-
or beta- (for alkyl from 0 to 40, optionally having halogen or
constituents) hydroxy, carboxy, carbonyl, polarizing or
water-insolubilizing/solubilizing thiol, mercapto, thiocarbonyl,
amino, imino, groups attached. (Not including ortho-, alpha-,
oximo, diazeno, or hydrazido substitution or beta-hydroxy, carboxy,
carbonyl, thiol, (N--N Tridentates). Also includes mercapto,
thiocarbonyl, amino, imino, oximo, trihydrazones. diazeno, or
hydrazido substitution.) Ligand can also contain nonbinding N, O,
S, or P atoms. N Valence Stabilizer #46:
N(--R--N.dbd.CR'R'').sub.3, where R, R', and R'' Schiff Bases with
three Imine (C.dbd.N) represent H, or any organic functional group
Groups and with ortho- or alpha- or beta- wherein the number of
carbon atoms ranges amino or imino or oximo or diazeno or from 0 to
40, optionally having halogen or hydrazido substitution (N--N
Tetradentates, polarizing or water-insolubilizing/solubilizing N--N
Pentadentates, or N--N Hexadentates) groups attached. (Must contain
ortho- or alpha- or beta-amino or imino or oximo or diazeno or
hydrazido substitution.) Ligand can also contain nonbinding N, O,
S, or P atoms. S Valence Stabilizer #1: Macrocyclic ligands
containing two, four, or six Macrocyclic, Macrobicyclic, and
thioketone binding sites to valence stabilize the Macropolycyclic
Oligothioketones central metal ion. Can include other (including
Catapinands, Cryptands, hydrocarbon or ring systems bound to this
Cyclidenes, and Sepulchrates) wherein all macrocyclic ligand, but
they do not coordinate Binding Sites are composed of Thioketones
with the stabilized, high valence metal ion. This (typically in the
beta position) (S--S ligand and/or attached, uncoordinating
Bidentates, S--S Tetradentates, and S--S hydrocarbons/rings may or
may not
have Hexadentates) halogen or polarizing or water-
insolubilizing/solubilizing groups attached. S Valence Stabilizer
#2: Macrocyclic ligands containing two, four, six, Macrocyclic,
Macrobicyclic, and or eight 1,1-dithiolene binding sites to valence
Macropolycyclic Dithiolenes (including stabilize the central metal
ion. Can include other Catapinands, Cryptands, Cyclidenes, and
hydrocarbon or ring systems bound to this Sepulchrates) wherein all
Binding Sites are macrocyclic ligand, but they do not coordinate
composed of alpha, alpha dithiols (meaning with the stabilized,
high valence metal ion. This two thiol groups on a single carbon
atom in ligand and/or attached, uncoordinating the ring) (S--S
Bidentates, S--S hydrocarbons/rings may or may not have
Tetradentates, and S--S Hexadentates) halogen or polarizing or
water- insolubilizing/solubilizing groups attached. S Valence
Stabilizer #3: RC(.dbd.S)--NR'--C(.dbd.S)--R'' for
Dithioimidodialdehydes, dithioimidodialdehydes, and
RC(.dbd.S)--NR'--NH-- Dithiohydrazidodialdehydes (thioacyl
C(.dbd.S)--R'' for dithiohydrazidodialdehydes thiohydrazides),
(thioacyl thiohydrazides), where R, R', and R''
Bis(dithioimidodialdehydes), represent H, NH.sub.2, or any organic
functional Bis(dithiohydrazidodialdehydes), group wherein the
number of carbon atoms Poly(dithioimidodialdehydes), and ranges
from 0 to 40, optionally having halogen
Poly(dithiohydrazidodialdehydes) (S--S or polarizing or water-
Bidentates, S--S Tridentates, S--S insolubilizing/solubilizing
groups attached. Tetradentates) Ligand can also contain nonbinding
N, O, S, or P atoms. S Valence Stabilizer #4:
R--O--C(.dbd.S)--NR'--C(.dbd.S)--O--R'' or R--S--C(.dbd.S)--
Dithioimidodicarbonic acids, NR'--C(.dbd.S)--S--R'' for
dithioimidodicarbonic Dithiohydrazidodicarbonic acids, acids, and
R--O--C(.dbd.S)--NR'--NH--C(.dbd.S)--O--R'' or
Bis(dithioimidodicarbonic acids),
R--S--C(.dbd.S)--NR'--NH--C(.dbd.S)--S--R'' for
Bis(dithiohydrazidodicarbonic acids), dithiohydrazidodicarbonic
acids, where R, R', Poly(dithioimidodicarbonic acids), and R''
represent H, NH.sub.2, or any organic
Poly(dithiohydrazidodicarbonic acids) and functional group wherein
the number of carbon derivatives thereof (S--S Bidentates, S--S
atoms ranges from 0 to 40, optionally having Tridentates, S--S
Tetradentates) halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #5:
R--C(.dbd.S)--CR'R''--C(.dbd.S)--R''' where R, R', R'',
1,3-Dithioketones (Dithio-beta-ketonates), and R''' represent H,
NH.sub.2, or any organic 1,3,5-Trithioketones, Bis(1,3- functional
group wherein the number of carbon Dithioketones), and Poly(1,3-
atoms ranges from 0 to 40, optionally having Dithioketones) (S--S
Bidentates, S--S halogen or polarizing or water- Tridentates, S--S
Tetradentates) insolubilizing/solubilizing groups attached. Ligand
can also contain nonbinding N, O, S, or P atoms. S Valence
Stabilizer #6: R--C(.dbd.S)--C(.dbd.S)--R' where R and R' represent
H, 1,2-Dithioketones (Dithiolenes, Dithio- NH.sub.2, or any organic
functional group wherein alpha-ketonates), 1,2,3-Trithioketones,
the number of carbon atoms ranges from 0 to Dithiotropolonates,
ortho-Dithioquinones, 40, optionally having halogen or polarizing
or Bis(1,2-Dithioketones), and Poly(1,2-
water-insolubilizing/solubilizing groups Dithioketones) (S--S
Bidentates, S--S attached. Ligand can also contain nonbinding N,
Tridentates, S--S Tetradentates) O, S, or P atoms. S Valence
Stabilizer #7:
RR'--N--C(.dbd.S)--CR''R'''--C(.dbd.S)--N--R''''R''''' where
Dithiomalonamides R, R', R'', R''',R'''', and R''''' represent H,
NH.sub.2, (Dithiomalonodiamides), or any organic functional group
wherein the Bis(dithiomalonamides), and number of carbon atoms
ranges from 0 to 40, Polydithiomalonamides (S--S Bidentates, S--
optionally having halogen or polarizing or S Tridentates, S--S
Tetradentates) water-insolubilizing/solubilizing groups attached.
Ligand can also contain nonbinding N, O, S, or P atoms. S Valence
Stabilizer #8: RR'--N--C(.dbd.S)--CR''R'''--C(.dbd.S)--R'''' where
R, R', 2-Thioacylthioacetamides, Bis(2- R'', R''', and R''''
represent H, NH.sub.2, or any thioacylthioacetamides), and Poly(2-
organic functional group wherein the number of
thioacylthioacetamides) (S--S Bidentates, S-- carbon atoms ranges
from 0 to 40, optionally S Tridentates, S--S Tetradentates) having
halogen or polarizing or water- insolubilizing/solubilizing groups
attached. Ligand can also contain nonbinding N, O, S, or P atoms. S
Valence Stabilizer #9: R--C(.dbd.S)--S--C(.dbd.S)--R' where R and
R' represent Dithioacyl sulfides, Bis(dithioacyl sulfides), H or
any organic functional group wherein the and Poly(dithioacyl
sulfides) (S--S number of carbon atoms ranges from 0 to 40,
Bidentates, S--S Tridentates, S--S optionally having halogen or
polarizing or Tetradentates) water-insolubilizing/solubilizing
groups attached. Ligand can also contain nonbinding N, O, S, or P
atoms. S Valence Stabilizer #10:
RR'--N--C(.dbd.S)--S--C(.dbd.S)--N--R''R''' where R, R',
Trithiodicarbonic Diamides, R'', and R''' represent H, NH.sub.2 or
any organic Bis(trithiodicarbonic diamides), and functional group
wherein the number of carbon Poly(trithiodicarbonic diamides) (S--S
atoms ranges from 0 to 40, optionally having Bidentates, S--S
Tridentates, S--S halogen or polarizing or water- Tetradentates)
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #11:
R--S--C(.dbd.S)--S--C(.dbd.S)--S--R' for Pentathio-, Tetrathio-, or
Trithiodicarbonic pentathiodicarbonic acids,
R--O--C(.dbd.S)--S--C(.dbd.S)-- Acids, Bis(pentathio-, tetrathio-,
or S--R' for tetrathiodicarbonic acids, and R--O--
trithiodicarbonic acids), Poly(pentathio-,
C(.dbd.S)--S--C(.dbd.S)--O--R' for pentathiodicarbonic tetrathio-,
or trithiodicarbonic acids), and acids, where R and R' represent H,
NH.sub.2 or any derivatives thereof (S--S Bidentates, S--S organic
functional group wherein the number of Tridentates, S--S
Tetradentates) carbon atoms ranges from 0 to 40, optionally having
halogen or polarizing or water- insolubilizing/solubilizing groups
attached. Ligand can also contain nonbinding N, O, S, or P atoms. S
Valence Stabilizer #12:
(R--O--)(R'--O--)P(.dbd.S)--P(.dbd.S)(--O--R'')(--O--R'''); (R--
Dithiohypophosphoric Acids,
O--)(R'--S--)P(.dbd.S)--P(.dbd.S)(--S--R'')(--O--R'''); or (R--
Bis(dithiohypophosphoric acids), and
S--)(R'--S--)P(.dbd.S)--P(.dbd.S)(--S--R'')(--S--R'''), where
Poly(dithiohypophosphoric acids), and R, R', R'', and R'''
represent H, NH.sub.2 or any derivatives thereof (S--S Bidentates,
S--S organic functional group wherein the number of Tridentates,
S--S Tetradentates) carbon atoms ranges from 0 to 40, optionally
having halogen or polarizing or water- insolubilizing/solubilizing
groups attached. Ligand can also contain nonbinding N, O, S, or P
atoms. Note: these ligands are not to be confused with
hypophosphorous acid derivatives (hypophosphites) (R--O--
)R''R'''P(.dbd.O) which are very reducing and therefore
unacceptable for stabilization of high valence states in metal
ions. S Valence Stabilizer #13:
(RR'--N--)(R''R'''--N--)P(.dbd.S)--P(.dbd.S)(--N--
Dithiohypophosphoramides, R''''R''''')(--N--R''''''R'''''''), where
R, R', R'', R''', Bis(dithiohypophosphoramides), and R'''', R''''',
R'''''', and R''''''' represent H, NH.sub.2 or
Poly(dithiohypophosphoramides) (S--S any organic functional group
wherein the Bidentates, S--S Tridentates, S--S number of carbon
atoms ranges from 0 to 40, Tetradentates) optionally having halogen
or polarizing or water-insolubilizing/solubilizing groups attached.
Ligand can also contain nonbinding N, O, S, or P atoms. Note: these
ligands are not to be confused with hypophosphorous acid
derivatives (hypophosphites) (R--O-- )R''R'''P(.dbd.O) which are
very reducing and therefore unacceptable for stabilization of high
valence states in metal ions. S Valence Stabilizer #14:
(R--O--)(R'--O--)P(.dbd.S)--NH--P(.dbd.S)(--O--R'')(--O--
Dithioimidodiphosphoric Acids, R''');
(R--O--)(R'--S--)P(.dbd.S)--NH--P(.dbd.S)(--S--R'')(--O--
Dithiohydrazidodiphosphoric Acids, R'''); or
(R--S--)(R'--S--)P(.dbd.S)--NH--P(.dbd.S)(--S--R'')(--
Bis(dithioimidodiphosphoric Acids), S--R''') for
dithioimidodiphosphoric acids, and --
Bis(dithiohydrazidodiphosphoric Acids), NH--NH-- derivatives for
Poly(dithioimidodiphosphoric Acids), dithiohydrazidodiphosphoric
acids, where R, Poly(dithiohydrazidodiphosphoric Acids), R', R'',
and R''' represent H, NH.sub.2 or any organic and derivatives
thereof (S--S Bidentates, S--S functional group wherein the number
of carbon Tridentates, S--S Tetradentates) atoms ranges from 0 to
40, optionally having halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #15:
(RR'--N--)(R''R'''--N--)P(.dbd.S)--NH--P(.dbd.S)(--N--
Dithioimidodiphosphoramides, R''''R''''')(--N--R''''''R''''''') for
Dithiohydrazidodiphosphoramides, dithioimidophosphoramides, and
(RR'--N-- Bis(dithioimidodiphosphoramides),
)(R''R'''--N--)P(.dbd.S)--NH--NH--P(.dbd- .S)(--N--
Bis(dithiohydrazidodiphosphoramides),
R''''R''''')(--N--R''''''R''''''') for
Poly(dithioimidodiphosphoramides), and
dithiohydrazidodiphosphoramides, where R, R',
Poly(dithiohydrazidodiphosphoramides) (S-- R'', R''', R'''',
R''''', R'''''', and R''''''' represent S Bidentates, S--S
Tridentates, S--S H, NH.sub.2 or any organic functional group
wherein Tetradentates) the number of carbon atoms ranges from 0 to
40, optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #16:
(RR'--N--)(R''R'''--N--)P(.dbd.S)--S--P(.dbd.S)(--N--
Dithiodiphosphoramides, R''''R''''')(--N--R''''''R'''''''), or
(RR'--N--)(R''R'''-- Bis(dithioiphosphoramides), and
N--)P(.dbd.S)--O--P(.dbd.S)(--N--R''''R''''')(--N--
Poly(dithiodiphosphoramides) (S--S R''''''R'''''''), where R, R',
R'', R''', R'''', R''''', Bidentates, S--S Tridentates, S--S
R'''''', and R''''''' represent H, NH.sub.2 or any Tetradentates)
organic functional group wherein the number of carbon atoms ranges
from 0 to 40, optionally having halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #17:
(R--O--)(R'--O--)P(.dbd.S)--O--P(.dbd.S)(--O--R'')(--O--R''');
Dithiodiphosphoric Acids,
(R--O--)(R'--O--)P(.dbd.S)--S--P(.dbd.S)(--O--R'')(--O--R''');
Bis(dithioiphosphoric Acids),
(R--O--)(R'--S--)P(.dbd.S)--O--P(.dbd.S)(--S--R'')(--O--R''');
Poly(dithiodiphosphoric Acids), and
(R--O--)(R'--S--)P(.dbd.S)--S--P(.dbd.S)(--S--R'')(--O--R'''); or
derivatives thereof (S--S Bidentates, S--S
(R--S--)(R'--S--)P(.dbd.S)--S--P(.dbd.S)(--S--R'')(--S--R'''),
Tridentates, S--S Tetradentates) where R, R', R'', R''', R'''',
R''''',
R'''''', and R''''''' represent H, NH.sub.2 or any organic
functional group wherein the number of carbon atoms ranges from 0
to 40, optionally having halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #18:
(O.dbd.)P(--S--R)(--S--R')(--S--R'') or (S.dbd.)P(--S--R)(--S--
Trithiophosphoric Acids R')(--O--R''), where R, R', and R''
represent H, (Phosphorotrithioic Acids), NH.sub.2 or any organic
functional group wherein Bis(trithiophosphoric acids), the number
of carbon atoms ranges from 0 to Poly(trithiophosphoric acids), and
40, optionally having halogen or polarizing or derivatives thereof
(S--S Bidentates, S--S water-insolubilizing/solubilizing groups
Tridentates, S--S Tetradentates) attached. Ligand can also contain
nonbinding N, O, S, or P atoms. S Valence Stabilizer #19:
(O.dbd.)P(--S--R)(--S--R')(--O--R'') or (S.dbd.)P(--S--R)(--O--
Dithiophosphoric Acids (Phosphorodithioic R')(--O--R''), where R,
R', and R'' represent H, Acids), Bis(dithiophosphoric acids),
NH.sub.2 or any organic functional group wherein
Poly(dithiophosphoric acids), and the number of carbon atoms ranges
from 0 to derivatives thereof (S--S Bidentates, S--S 40, optionally
having halogen or polarizing or Tridentates, S--S Tetradentates)
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #20:
(S.dbd.)P(--S--R)(--S--R')(--S--R''), where R, R', and R''
Tetrathiophosphoric Acids represent H, NH.sub.2 or any organic
functional (Phosphorotetrathioic Acids), group wherein the number
of carbon atoms Bis(tetrathiophosphoric acids), ranges from 0 to
40, optionally having halogen Poly(tetrathiophosphoric acids), and
or polarizing or water- derivatives thereof (S--S Bidentates, S--S
insolubilizing/solubilizing groups attached. Tridentates, S--S
Tetradentates) Ligand can also contain nonbinding N, O, S, or P
atoms. S Valence Stabilizer #21: (O)P(--S--S--R)(--S--R')(--S--R'')
or (S.dbd.)P(--S--S-- Phosphoro(dithioperoxo)dithioic Acids,
R)(--S--R')(--O--R''), where R, R', and R''
Bis[phosphoro(dithioperoxo)dithioic represent H, NH.sub.2 or any
organic functional Acids], group wherein the number of carbon atoms
Poly[phosphoro(dithioperoxo)dithioic ranges from 0 to 40,
optionally having halogen Acids], and derivatives thereof (S--S or
polarizing or water- Bidentates, S--S Tridentates, S--S
insolubilizing/solubilizing groups attached. Tetradentates) Ligand
can also contain nonbinding N, O, S, or P atoms. S Valence
Stabilizer #22: (O.dbd.)P(--S--S--R)(--S--R')(--O--R'') or
(S.dbd.)P(--S--S-- Phosphoro(dithioperoxo)thioic Acids,
R)(--O--R')(--O--R''), where R, R', and R''
Bis[phosphoro(dithioperoxo)thioic Acids], represent H, NH.sub.2 or
any organic functional Poly[phosphoro(dithioperoxo)thioic Acids],
group wherein the number of carbon atoms and derivatives thereof
(S--S Bidentates, S--S ranges from 0 to 40, optionally having
halogen Tridentates, S--S Tetradentates) or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #23:
(S.dbd.)P(--S--S--R)(--S--R')(--S--R''), where R, R', and
Phosphoro(dithioperoxo)trithioic Acids, R'' represent H, NH.sub.2
or any organic functional Bis[phosphoro(dithioperoxo)trithioic
group wherein the number of carbon atoms Acids], ranges from 0 to
40, optionally having halogen Poly[phosphoro(dithioperoxo)trithioic
or polarizing or water- Acids], and derivatives thereof (S--S
insolubilizing/solubilizing groups attached. Bidentates, S--S
Tridentates, S--S Ligand can also contain nonbinding N, O, S, or
Tetradentates) P atoms. S Valence Stabilizer #24:
R--CR'(--SH)--CH.sub.2--C(.dbd.S)--R'', where R, R', and
Beta-Mercaptothioketones, Beta- R'' represent H, NH.sub.2 or any
organic functional Mercaptothioaldehydes, Bis(beta- group wherein
the number of carbon atoms mercaptothioketones), Bis(beta- ranges
from 0 to 40, optionally having halogen mercaptothioaldehydes),
Poly(beta- or polarizing or water- mercaptothioketones), and
Poly(beta- insolubilizing/solubilizing groups attached.
mercaptothioaldehydes) (S--S Bidentates, S-- Ligand can also
contain nonbinding N, O, S, or S Tridentates, S--S Tetradentates) P
atoms. S Valence Stabilizer #25:
RR'--N--CH(--SH)--NR''--C(.dbd.S)--NR'''R'''', where
N--(Aminomethylthiol)thioureas [N-- R, R', R'', R''', and R''''
represent H, NH.sub.2 or any (Aminomercaptomethyl)thioureas],
Bis[N-- organic functional group wherein the number of
(aminomethylthiol)thioureas], and Poly[N-- carbon atoms ranges from
0 to 40, optionally (aminomethylthiol)thioureas] (S--S having
halogen or polarizing or water- Bidentates, S--S Tridentates, S--S
insolubilizing/solubilizing groups attached. Tetradentates) Ligand
can also contain nonbinding N, O, S, or P atoms. S Valence
Stabilizer #26: RR'--N--C(.dbd.S)--C(.dbd.S)--N--R''R''', where R,
R', Dithiooxamides, Bis(dithiooxamides), and R'', and R'''
represent H, NH.sub.2 or any organic Poly(dithiooxamides) (S--S
Bidentates, S--S functional group wherein the number of carbon
Tridentates, S--S Tetradentates) atoms ranges from 0 to 40,
optionally having halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #27:
RR'--C.dbd.C(--S.sup.-)(--S.sup.-), where R and R' represent H,
1,1-Dithiolates, Bis(1,1-dithiolates), and NH.sub.2 or any organic
functional group wherein Poly(1,1-dithiolates) (S--S Bidentates and
S-- the number of carbon atoms ranges from 0 to S Tetradentates)
40, optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #28:
R--C(.dbd.S)(--S--R') for dithiomonocarboxylic acids,
Dithiomonocarboxylic Acids, Tri- and and
(R--S--)(S.dbd.)C--R'--C(.dbd.S)(--S--R'') for tri- and
Tetrathiodicarboxylic Acids, tetrathiodicarboxylic acids, where R,
R', and R'' Bis(dithiomonocarboxylic Acids), Bis(tri- represent H,
NH.sub.2 or any organic functional and tetrathiodicarboxylic
acids), group wherein the number of carbon atoms
Poly(dithiomonocarboxylic acids), Poly(tri- ranges from 0 to 40,
optionally having halogen and tetrathiodicarboxylic acids), and or
polarizing or water- derivatives thereof (S--S Bidentates and S--S
insolubilizing/solubilizing groups attached. Tetradentates) Ligand
can also contain nonbinding N, O, S, or P atoms. S Valence
Stabilizer #29: R--C(.dbd.S)(--S--S--R') for perthiomonocarboxylic
Perthiomonocarboxylic Acids, acids, and
(R--S--S--)(S.dbd.)C--R'--C(.dbd.S)(--S--S--R'')
Perthiodicarboxylic Acids, for perthiodicarboxylic acids, where R,
R', and Bis(perthiomonocarboxylic acids), R'' represent H, NH.sub.2
or any organic functional Bis(perthiodicarboxylic acids), group
wherein the number of carbon atoms Poly(perthiomonocarboxylic
acids), ranges from 0 to 40, optionally having halogen
Poly(perthiodicarboxylic acids), and or polarizing or water-
derivatives thereof (S--S Bidentates and S--S
insolubilizing/solubilizing groups attached. Tetradentates) Ligand
can also contain nonbinding N, O, S, or P atoms. S Valence
Stabilizer #30: R--S--C(.dbd.S)--O--R' orR--S--C(.dbd.O)--S--R' for
Dithiocarbonates, Trithiocarbonates, dithiocarbonates,
R--S--C(.dbd.S)--S--R' for Perthiocarbonates,
Bis(dithiocarbonates), trithiocarbonates, and
R--S--S--C(.dbd.S)--S--R' for Bis(trimiocarbonates), and
perthiocarbonates, where R, and R' represent H,
Bis(perthiocarbonates) (S--S Bidentates and NH.sub.2 or any organic
functional group wherein S--S Tetradentates) the number of carbon
atoms ranges from 0 to 40, optionally having halogen or polarizing
or water-insolubilizing/solubilizing groups attached. Ligand can
also contain nonbinding N, O, S, or P atoms. S Valence Stabilizer
#31: RR'N.sup.+.dbd.C(SH)(SH), where R and R' represent
Dithiocarbamates, Bis(dithiocarbamates), H, OH, SH, OR'' (R'' .dbd.
C.sub.1-C.sub.30 alkyl or aryl), and Poly(dithiocarbamates)
(including N-- SR'' (R'' .dbd. C.sub.1-C.sub.30 alkyl or aryl),
NH.sub.2 or any hydroxydithiocarbamates and N-- organic functional
group wherein the number of mercaptodithiocarbamates) (S--S
Bidentates, carbon atoms ranges from 0 to 40, optionally S--S
Tridentates, and S--S Tetradentates) having halogen or polarizing
or water- insolubilizing/solubilizing groups attached. Ligand can
also contain nonbinding N, O, S, or P atoms. S Valence Stabilizer
#32: RR'N--NR''--C(.dbd.S)(SH), where R and R' Dithiocarbazates
(Dithiocarbazides), represent H, NH.sub.2 or any organic functional
Bis(dithiocarbazates), and group wherein the number of carbon atoms
Poly(dithiocarbazates) (S--S Bidentates, S--S ranges from 0 to 40,
optionally having halogen Tridentates, and S--S Tetradentates; or
or polarizing or water- possibly N--S Bidentates, N--S Tridentates,
insolubilizing/solubilizing groups attached. and N--S
Tetradentates) Ligand can also contain nonbinding N, O, S, or P
atoms. N--S Valence Stabilizer #1:
RR'--N--C(.dbd.NH)--S--S--C(.dbd.NH)--NR''R''', where Diformamidine
Bisulfides R, R', R'', and R''' represent H, NH.sub.2, or any
(Thioperoxydicarbonimidic Diamides or organic functional group
wherein the number of Dihydrazides), Thioperoxytricarbonimidic
carbon atoms ranges from 0 to 40, optionally Diamides or
Dihydrazides, having halogen or polarizing or water-
Thioperoxytetracarbonimidic Diamides or insolubilizing/solubilizing
groups attached. Dihydrazides, Bis(diformamidine Ligand can also
contain nonbinding N, O, S, or disulfides), and Poly(diformamidine
P atoms. disulfides) (N--S Bidentates, N--S Tridentates, N--S
Tetradentates) N--S Valence Stabilizer #2:
RR'--N--C(.dbd.NH)--S--CS--NR''R''', where R, R',
S--Amidinodithiocarbamates, Bis(S-- R'', and R''' represent H,
NH.sub.2 or any organic amidinodithiocarbamates), and Poly(S--
functional group wherein the number of carbon
amidinodithiocarbamates) (N--S Bidentates atoms ranges from 0 to
40, optionally having and N--S Tetradentates) halogen or polarizing
or water- insolubilizing/solubilizing groups attached. Ligand can
also contain nonbinding N, O, S, or P atoms. N--S Valence
Stabilizer #3: RR'--N--C(.dbd.NH)--O--CS--NR''R''', where R, R',
O-Amidinothiocarbamates, Bis(O- R'', and R''' represent H, NH.sub.2
or any organic amidinothiocarbamates), and Poly(O- functional group
wherein the number of carbon amidinothiocarbamates) (N--S
Bidentates atoms ranges from 0 to 40, optionally having and N--S
Tetradentates) halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--S Valence Stabilizer #4:
RR'--N--C(.dbd.NH)--S--S--CS--NR''R''', where R, R',
S-Amidinoperoxymiocarbamates, Bis(S- R'', and R''' represent H,
NH.sub.2 or any organic amidinoperoxythiocarbamates), and Poly(S-
functional group wherein the number of carbon
amidinoperoxythiocarbamates) (N--S atoms ranges from 0 to 40,
optionally having Bidentates and N--S Tetradentates) halogen or
polarizing or water- insolubilizing/solubilizing groups attached.
Ligand can also contain nonbinding N, O, S, or P atoms. N--S
Valence Stabilizer #5: (NH.dbd.)P(--SR)(--OR')(--OR'') for
Phosphorimidothioic Acid; phosphorimidothioic acid,
(NH.dbd.)P(--SR)(--SR')(-- Phosphorimidodithioic Acid; OR'') for
phosphorimidodithioic acid, (NH.dbd.)P(-- Phosphorimidotrithioic
Acid; SR)(--SR')(--SR'') for phosphorimidotrithioic
Bis(Phosphorimidothioic Acid); acid, where R, R', and R'' represent
H, NH.sub.2 or Bis(Phosphorimidodithioic Acid); any organic
functional group wherein the Bis(Phosphorimidotrithioic Acid);
number of carbon atoms ranges from 0 to 40,
Poly(Phosphorimidothioic Acid); optionally having halogen or
polarizing or Poly(Phosphorimidodithioic Acid);
water-insolubilizing/solubilizing groups
Poly(Phosphorimidotrithioic Acid); and attached. Ligand can also
contain nonbinding N, derivatives thereof (N--S Bidentates and N--S
O, S, or P atoms. Tetradentates) N--S Valence Stabilizer #6:
(S.dbd.)P(--NRR')(--NR''R''')(--NR''''R'''''), where R,
Phosphorothioic Triamides, R', R'', R''', R'''', and R'''''
represent H, NH.sub.2 or Bis(phosphorothioic triamides), and any
organic functional group wherein the Poly(phosphorothioic
triamides) (N--S number of carbon atoms ranges from 0 to 40,
Bidentates and N--S Tetradentates) optionally having halogen or
polarizing or water-insolubilizing/solubilizing groups attached.
Ligand can also contain nonbinding N, O, S, or P atoms. N--S
Valence Stabilizer #7: (S.dbd.)P(--NRR')(--SR'')(--SR''') for
Phosphoramidotrithioic Acid, phosphoramidotrithioic acid, and
(S.dbd.)P(-- Phosphorodiamidodithioic Acid,
NRR')(--NR''R''')(--SR'''') for Bis(phosphoramidotrithioic acid),
phosphorodiamidodithioic acid, where R, R',
Bis(phosphorodiamidodithioic acid), R'', R''', and R'''' represent
H, NH.sub.2 or any poly(phosphoramidotrithioic acid), organic
functional group wherein the number of
poly(phosphorodiamidodithioic acid), and carbon atoms ranges from 0
to 40, optionally derivatives thereof (N--S Bidentates and N--S
having halogen or polarizing or water- Tetradentates)
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--S Valence Stabilizer #8:
(O.dbd.)P(--NRR')(--SR'')(--OR''') or (S.dbd.)P(--
Phosphoramidothioic Acid, NRR')(--OR'')(--OR''') for
phosphoramidothioic Phosphoramidodithioic Acid, acid;
(O.dbd.)P(--NRR')(--SR'')(--SR''') or (S.dbd.)P(--
Phosphorodiamidothioic Acid, NRR')(--SR'')(--OR''') for
Bis(Phosphoramidothioic Acid), phosphoramidodithioic acid;
(O.dbd.)P(--NRR')(-- Bis(Phosphoramidodithioic Acid),
NR''R''')(--SR'''') or (S.dbd.)P(--NRR')(--NR''R''')(--
Bis(Phosphorodiamidothioic Acid), OR'''') for
phosphorodiamidothioic acid, where Poly(Phosphoramidothioic Acid),
R, R', R'', R''', and R'''' represent H, NH.sub.2 or any
Poly(Phosphoramidodithioic Acid), and organic functional group
wherein the number of Poly(Phosphorodiamidothioic Acid) (N--S
carbon atoms ranges from 0 to 40, optionally Bidentates and N--S
Tetradentates) having halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--S Valence Stabilizer #9:
R'--C(.dbd.S)--N.dbd.C(--R)(--NHR''), where R is an N-Thioacyl
7-Aminobenzylidenimines (N--S aromatic derivative (i.e.,
--C.sub.6H.sub.5), and R' and R'' Bidentates or N--S Tetradentates)
represent H, NH.sub.2, or any organic functional group wherein the
number of carbon atoms ranges from 0 to 40, optionally having
halogen or polarizing or water- insolubilizing/solubilizing groups
attached. Ligand can also contain nonbinding N, O, S, or P atoms.
N--S Valence Stabilizer #10: R--C(.dbd.S)--NR'--OH or
R--C(--SH).dbd.N--OH, where Thiohydroxamates (Thiohydroxylamines),
R and R' represent H, NH.sub.2, or any organic
Bis(thiohydroxamates), and functional group wherein the number of
carbon Poly(thiohydroxamates) (N--S Bidentates, atoms ranges from 0
to 40, optionally having N--S Tetradentates, and N--S Hexadentates)
halogen or polarizing or water- insolubilizing/solubilizing groups
attached. Ligand can also contain nonbinding N, O, S, or P atoms.
N--S Valence Stabilizer #11: R--CH(--NHR')--C(.dbd.S)(--OH) or
R--CH(--NHR')-- Alpha- or ortho-Aminothiocarboxylic C(.dbd.S)(--SH)
for aminothiocarboxylic acids, and Acids, and alpha- or ortho-
(HO--)(S.dbd.)C--CH(--NHR)--R'--CH(--NHR'')-- Aminothiodicarboxylic
Acids, and C(.dbd.S)(--OH) or (HS--)(S.dbd.)C--CH(--NHR)--R'--
derivatives thereof (N--S Bidentates, N--S
CH(--NHR'')--C(.dbd.S)(--SH) for Tridentates, and N--S
Tetradentates) aminothiodicarboxylic acids, where R, R', and R''
represent any organic functional group wherein the number of carbon
atoms ranges from 1 to 40, optionally having halogen or polarizing
or water-insolubilizing/solubilizing groups attached. Ligand can
also contain nonbinding N, O, S, or P atoms. N--S Valence
Stabilizer #12: RR'--N--C(.dbd.S)--NR''--N.dbd.CR'''R'''', where R,
R', Thiosemicarbazones, R'', R''', and R'''' represent H, or any
organic Bis(thiosemicarbazones), and functional group wherein the
number of carbon Poly(thiosemicarbazones) (N--S Bidentates, atoms
ranges from 0 to 40, optionally having N--S Tetradentates, and N--S
Hexadentates) halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--S Valence Stabilizer
#13: R--C(.dbd.S)--NR'--N.dbd.CR''R''', where R, R', R'', and
Thioacyl hydrazones, Bis(thioacyl R''' represent H, or any organic
functional hydrazones), and Poly(thioacyl hydrazones) group wherein
the number of carbon atoms (N--S Bidentates, N--S Tetradentates,
and N-- ranges from 0 to 40, optionally having halogen S
Hexadentates) or polarizing or water- insolubilizing/solubilizing
groups attached. Ligand can also contain nonbinding N, O, S, or P
atoms. N--S Valence Stabilizer #14:
R--N.dbd.N--C(.dbd.S)--NR'--NR''R''', where R, R', R'',
Thiocarbazones (Diazenecarbothioic and R''' represent H, or any
organic functional hydrazides), Bis(thiocarbazones), and group
wherein the number of carbon atoms Poly(thiocarbazones) (N--S
Bidentates, N--S ranges from 0 to 40, optionally having halogen
Tetradentates, and N--S Hexadentates) or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--S Valence Stabilizer
#15: R--N.dbd.N--R', where R, and R' represent H or any Azo
compounds with thiol or mercapto or organic functional group
wherein the number of thiocarbonyl substitution at the ortho- (for
carbon atoms ranges from 0 to 40, optionally aryl) or alpha- or
beta- (for alkyl) positions, having halogen or polarizing or water-
Bis[o-(HS--) or alpha- or beta-(HS--)azo
insolubilizing/solubilizing groups attached. compounds], or
Poly[o-(HS--) or alpha- or (Must include ortho-thio, mercapto, or
beta-(HS--)azo compounds) (N--S thiocarbonyl substituted aryl azo
compounds, Bidentates, N--S Tridentates, N--S and alpha- or
beta-thio, mercapto, or Tetradentates, or N--S Hexadentates)
thiocarbonyl alkyl azo compounds.) Ligand can also contain
nonbinding N, O, S, or P atoms. N--S Valence Stabilizer #16:
R--N.dbd.N--C(.dbd.S)--NR'R'' for Diazeneformothioamides,
diazeneformothioamides, and R--N.dbd.N--CR'R''--
Diazeneacetothioamides, C(.dbd.S)--NR'''R'''' for
diazeneacetothioamides, Bis(diazeneformothioamides), where R, R',
R'', R''', and R'''' represent H, Bis(diazeneacetothioamides),
NH.sub.2, or any organic functional group wherein
Poly(diazeneformothioarnides), and the number of carbon atoms
ranges from 0 to Poly(diazeneacetothioamides) (N--S 40, optionally
having halogen or polarizing or Bidentates, N--S Tetradentates, and
N--S water-insolubilizing/solubilizing groups Hexadentates)
attached. Ligand can also contain nonbinding N, O, S, or P atoms.
N--S Valence Stabilizer #17: R--N.dbd.N--C(.dbd.S)--O--R' or
R--N.dbd.N--CR'R''--C(.dbd.S)-- Diazenecarbothioic acids, O--R'''
for diazenecarbothioic acids, and R-- Diazenecarbodithioic acids,
N.dbd.N--C(.dbd.S)--S--R' or R--N.dbd.N--CR'R''--C(.dbd.S)--S--
Bis(diazenecarbothioic acids), R''' for diazenecarbodithoic acids,
where R, R', Bis(diazenecarbodithioic acids), R'', and R'''
represent H, NH.sub.2, or any organic Poly(diazenecarbothioic
acids), functional group wherein the number of carbon
Poly(diazenecarbodithioic acids) and atoms ranges from 0 to 40,
optionally having derivatives thereof (N--S Bidentates, N--S
halogen or polarizing or water- Tetradentates, N--S Hexadentates)
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--S Valence Stabilizer
#18: R--N.dbd.N--C(.dbd.S)--R' for Diazeneformothioaldehydes,
diazeneformothioaldehydes, and R--N.dbd.N--
Diazeneacetothioaldehydes, CR'R''--C(.dbd.S)--R''' for
Bis(diazeneformothioaldehydes), diazeneacetothioaldehydes, where R,
R', R'', Bis(diazeneacetothioaldehydes), and R''' represent H,
NH.sub.2, or any organic Poly(diazeneformothioaldehydes), and
functional group wherein the number of carbon
Poly(diazeneacetothioaldehydes) (N--S atoms ranges from 0 to 40,
optionally having Bidentates, N--S Tetradentates and N--S halogen
or polarizing or water- Hexadentates) insolubilizing/solubilizing
groups attached. Ligand can also contain nonbinding N, O, S, or P
atoms. N--S Valence Stabilizer #19:
RR'--N--C(.dbd.S)--N.dbd.N--C(.dbd.S)--NR''R''' or RR'--N--
Diazenediformothioamides, C(.dbd.S)--N.dbd.N--C(.dbd.O)--NR''R'''
for Diazenediacetothioamides, diazenediformothioamides, and
RR'--N--C(.dbd.S)-- Bis(diazenediformothioamides),
CR''R'''--N.dbd.N--CR''''R'''''--C(.dbd.S)-- -NR''''''R''''''' or
Bis(diazenediacetothioamides),
RR'--N--C(.dbd.S)--CR''R'''--N.dbd.N--CR'''- 'R'''''--C(.dbd.O)--
Poly(diazenediformothioamides), and NR''''''R''''''' for
diazenediacetothioamides, Poly(diazenediacetothioamides) (N--S
where R, R', R'', R''', R'''', R''''', R'''''', and Tridentates and
N--S Hexadentates) R''''''' represent H, NH.sub.2, or any organic
functional group wherein the number of carbon atoms ranges from 0
to 40, optionally having halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--S Valence Stabilizer
#20: R--O--C(.dbd.S)--N.dbd.N--C(.dbd.S)--O--R', R--O--C(.dbd.S)--
Diazenedicarbothioic acids,
CR'R''--N.dbd.N--CR'''R''''--C(.dbd.S)--O--R''''', R--O--
Diazenedicarbodithioic acids, C(.dbd.S)--N.dbd.N--C(.dbd.O)--O--R',
or R--O--C(--S)-- Bis(diazenedicarbothioic acids),
CR'R''--N.dbd.N--CR'''R''''--C(.dbd.O)--O--R''''' for
Bis(diazenedicarbodithioic acids), diazenedicarbothioic acids, and
R--S--C(.dbd.S)-- Poly(diazenedicarbothioic acids),
N.dbd.N--C(.dbd.S)--S--R' or R--S--C(.dbd.S)--CR'R''--N.dbd.N--
Poly(diazenedicarbodithioic acids) and
CR'''R''''--C(.dbd.S)--S--R''''' for derivatives thereof (N--S
Tridentates and N-- diazenedicarbodithoic acids, where R, R', R'',
S Hexadentates) R''', R'''', and R''''' represent H, NH.sub.2, or
any organic functional group wherein the number of carbon atoms
ranges from 0 to 40, optionally having halogen or polarizing or
water- insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--S Valence Stabilizer
#21: RC(.dbd.S)--N.dbd.N--C(.dbd.S)--R' or RC(.dbd.S)--N.dbd.N--
Diazenediformothioaldehydes, C(.dbd.O)--R' for
diazenediformothioaldehydes, and Diazenediacetothioaldehydes,
RC(.dbd.S)--CR'R''--N.dbd.N--CR'''R''''--C(.d- bd.S)--R''''' or
Bis(diazenediformothioaldehydes),
RC(.dbd.S)--CR'R''--N.dbd.N--CR'''R''''-- -C(.dbd.O)--R''''' for
Bis(diazenediacetothioaldehydes), diazenediacetothioaldehydes,
where R, R', R'', Poly(diazenediformothioaldehydes), and R''',
R'''', and R''''' represent H, NH.sub.2, or any
Poly(diazenediacetothioaldehydes) (N--S organic functional group
wherein the number of Tridentates and N--S Hexadentates) carbon
atoms ranges from 0 to 40, optionally having halogen or polarizing
or water- insolubilizing/solubilizing groups attached. Ligand can
also contain nonbinding N, O, S, or P atoms. N--S Valence
Stabilizer #22: R--N.dbd.N--CR'.dbd.N--NR''R''', where R, R', R'',
and Ortho-thio (or -mercapto) Substituted R''' represent H, or any
organic functional Formazans, Bis(o-thio or -mercapto group wherein
the number of carbon atoms substituted formazans), and Poly(o-thio
or - ranges from 0 to 40, optionally having halogen mercapto
substituted formazans) (N--S or polarizing or water- Bidentates,
N--S Tridentates, N--S insolubilizing/solubilizing groups attached.
Tetradentates, and N--S Hexadentates) (Must include ortho-thio or
mercapto substituted aryl R derivatives, and beta-thio or mercapto
substituted alkyl R derivatives.) Ligand can also contain
nonbinding N, O, S, or P atoms. N--S Valence Stabilizer #23:
RR'C.dbd.N--N.dbd.CR''R''' or RR'C.dbd.N--NR''R''' (for Ortho-thio
(or -mercapto) Substituted ketazines), where R, R', R'', and R'''
represent Azines (including ketazines), Bis(o-thio or H, or any
organic functional group wherein the mercapto substituted azines),
and Poly(o- number of carbon atoms ranges from 0 to 40, thio or
mercapto substituted azines) (N--S optionally having halogen or
polarizing or Bidentates, N--S Tridentates, N--S
water-insolubilizing/solubilizing groups Tetradentates, and N--S
Hexadentates) attached. (Must include ortho-thio or mercapto
substituted aryl R derivatives, and beta-thio or mercapto
substituted alkyl R derivatives.) Ligand can also contain
nonbinding N, O, S, or P atoms. N--S Valence Stabilizer #24:
RR'C.dbd.N--R'', where R, R', and R'' represent H, Schiff Bases
with one Imine (C.dbd.N) Group or any organic functional group
wherein the and with ortho- or alpha- or beta-thio or number of
carbon atoms ranges from 0 to 40, mercapto or thiocarbonyl
substitution (N--S optionally having halogen or polarizing or
Bidentates, N--S Tridentates, N--S
water-insolubilizing/solubilizing groups Tetradentates, N--S
Pentadentates, or N--S attached. (Must contain ortho- or alpha- or
beta- Hexadentates). Also includes Schiff Bases thio or mercapto or
thiocarbonyl substitution.) derived from the reaction of carbonyl
Ligand can also contain nonbinding N, O, S, or compounds with
dithiocarbazates, and P atoms. hydrazones with ortho--S
substitution. N--S Valence Stabilizer #25:
RR'C.dbd.N--R''--N.dbd.CR'''R'''' or R--N.dbd.C--R'--C.dbd.N--
Schiff Bases with two Imine (C.dbd.N) Groups R' or
RC.dbd.N--R'--N.dbd.CR'', where R, R', R'', R''', and with ortho-
or alpha- or beta-thio or and R'''' represent H, or any organic
functional mercapto or thiocarbonyl substitution (N--S group
wherein the number of carbon atoms Tridentates, N--S Tetradentates,
N--S ranges from 0 to 40, optionally having halogen Pentadentates,
or N--S Hexadentates). Also or polarizing or water- includes Schiff
Bases derived from the insolubilizing/solubilizing groups attached.
reaction of carbonyl compounds with (Must contain ortho- or alpha-
or beta-thio or dithiocarbazates, and hydrazones with mercapto or
thiocarbonyl substitution.) Ligand ortho-S substitution. can also
contain nonbinding N, O, S, or P atoms. N--S Valence Stabilizer
#26: N(--R--N.dbd.CR'R'').sub.3, where R, R', and R'' Schiff Bases
with three Imine (C.dbd.N) represent H, or any organic functional
group Groups and with ortho- or alpha- or beta- wherein the number
of carbon atoms ranges thio or mercapto or thiocarbonyl from 0 to
40, optionally having halogen or substitution (N--S Tetradentates,
N--S polarizing or water-insolubilizing/solubilizing Pentadentates,
or N--S Hexadentates). Also groups attached. (Must contain ortho-
or alpha- includes Schiff Bases derived from the or beta-thio or
mercapto or thiocarbonyl reaction of carbonyl compounds with
substitution.) Ligand can also contain dithiocarbazates, and
hydrazones with nonbinding N, O, S, or P atoms. ortho-S
substitution. N--S Valence Stabilizer #27:
[R--CR'(--NR''R''')].sub.x--R''''--[C(-- Thioalkyl Amines
(Aminothiols or SR''''')R''''''R'''''''].sub.y,
[R--CR'(--NR''R''')].sub.x--R''''-- Aminodisulfides) and Thioalkyl
Imines [C(--S--S--R''''')R''''''R'''''''].sub.y, or [R--CR'(--
(Iminothiols or Iminodisulfides) (N--S
NR''R''')].sub.x--R''''--[C(.dbd.S)R'''''].sub.y for thioalkyl
Bidentates, N--S Tridentates, N--S amines; and
[R--C(.dbd.NR')].sub.x--R''--[C(-- Tetradentates, and N--S
Hexadentates) SR''')R''''R'''''].sub.y,
[R--C(.dbd.NR')].sub.x--R''--[C(--S-- SR''')R''''R'''''].sub.y, or
[R--C(.dbd.NR')].sub.x--R''-- [C(.dbd.S)R'''].sub.y for thioalkyl
imines, where R, R', R'', R''', R'''', R''''', R'''''', and
R''''''' represent H, NH.sub.2, or any organic functional group
wherein the number of carbon atoms ranges from 0 to 40, optionally
having halogen or polarizing or water-insolubilizing/solubilizing
groups attached, and x and y = 1-6. Ligand can also contain
nonbinding N, O, S, or P atoms. N--S Valence Stabilizer #28:
[R(--NR'R'')(--SR''')], [R(--NR'R'')(--S--S--R''')], Thioaryl
Amines and Thioaryl Imines (N--S [R(--NR'R'')(--C(.dbd.S)R'''],
[R(--NR'R'').sub.x].sub.2S, [R(-- Bidentates, N--S Tridentates,
N--S NR'R'').sub.x].sub.2-3R'''(--SR'''').sub.y,
[R(--SR').sub.x].sub.2-3R''(-- Tetradentates, and N--S
Hexadentates) NR'''R'''').sub.y, [R(--NR'R'').sub.x].sub.2S.sub.2,
and [R(-- NR'R'').sub.x].sub.2R'''(C(.dbd.S)).sub.yR'''' for
thioaryl amines; and [R(--SR').sub.x].sub.2NH or
[R(--SR').sub.x].sub.2NHNH for thioaryl imines, where R, R', R'',
R''', and R'''' represent H, NH.sub.2, or any organic functional
group wherein the number of carbon atoms ranges from 0 to 40,
optionally having halogen or polarizing or water-
insolubilizing/solubilizing groups attached, and x = 0-2 and y =
1-4. Ligand can also contain nonbinding N, O, S, or P atoms. N--S
Valence Stabilizer #29: Five membered heterocyclic ring(s)
containing Five-Membered Heterocyclic Rings one, two, three, or
four nitrogen atoms. In containing One, Two, Three, or Four
addition, ligand contains additional sulfur- Nitrogen Atoms at
least one additional containing substituents (usually thiols,
Sulfur Atom Binding Site not in a Ring (N-- mercaptans, disulfides,
or thiocarbonyls) that S Bidentates, N--S Tridentates, N--S
constitute S binding sites. Can include other Tetradentates, or
N--S Hexadentates) ring systems bound to the heterocyclic ring or
to the S-containing substituent, but they do not coordinate with
the stabilized, high valence metal ion. Ring(s) can also contain O,
S, or P atoms. This 5-membered ring(s) and/or attached,
uncoordinating rings and/or S- containing substituent(s) may or may
not have halogen or polarizing or water-
insolubilizing/solubilizing groups attached. N--S Valence
Stabilizer #30: Six membered heterocyclic ring(s) containing
Six-Membered Heterocyclic Rings one, two, three, or four nitrogen
atoms. In containing One, Two, Three, or Four addition, ligand
contains additional sulfur- Nitrogen Atoms at least one additional
containing substituents (usually thiols, Sulfur Atom Binding Site
not in a Ring (N-- mercaptans, disulfides, or thiocarbonyls) that S
Bidentates, N--S Tridentates, N--S constitute S binding sites. Can
include other Tetradentates, or N--S Hexadentates) ring systems
bound to the heterocyclic ring or to the S-containing substituent,
but they do not coordinate with the stabilized, high valence metal
ion. Ring(s) can also contain O, S, or P atoms. This 6-membered
ring(s) and/or attached, uncoordinating rings and/or S- containing
substituent(s) may or may not have halogen or polarizing or water-
insolubilizing/solubilizing groups attached. N--S Valence
Stabilizer #31: Five membered heterocyclic ring(s) containing
Five-Membered Heterocyclic Rings one or two sulfur atoms. In
addition, ligand containing One or Two Sulfur Atoms at contains
additional nitrogen-containing least one additional Nitrogen Atom
Binding substituents (usually amines, imines, or Site not in a Ring
(N--S Bidentates, N--S hydrazides) that constitute N binding sites.
Can Tridentates, N--S Tetradentates, or N--S include other ring
systems bound to the Hexadentates) heterocyclic ring or to the
N-containing substituent, but they do not coordinate with the
stabilized, high valence metal ion. Ring(s) can also contain O, S,
or P atoms. This 5-membered ring(s) and/or attached, uncoordinating
rings and/or N-containing substituent(s) may or may not have
halogen or polarizing or water- insolubilizing/solubilizing groups
attached. N--S Valence Stabilizer #32: Six membered heterocyclic
ring(s) containing Six-Membered Heterocyclic Rings one or two
sulfur atoms. In addition, ligand containing One or Two Sulfur
Atoms at contains additional nitrogen-containing least one
additional Nitrogen Atom Binding substituents (usually amines,
imines, or Site not in a Ring (N--S Bidentates, N--S hydrazides)
that constitute N binding sites. Can Tridentates, N--S
Tetradentates, or N--S include other ring systems bound to the
Hexadentates) heterocyclic ring or to the N-containing substituent,
but they do not coordinate with the stabilized, high valence metal
ion. Ring(s) can also contain O, S, or P atoms. This 6-membered
ring(s) and/or attached, uncoordinating rings and/or N-containing
substituent(s) may or may not have halogen or polarizing or water-
insolubilizing/solubilizing groups attached. N--S Valence
Stabilizer #33: Five membered heterocyclic ring(s)
containing Five-Membered Heterocyclic Rings one, two, three, or
four nitrogen atoms. In containing One, Two, Three, or Four
addition, ligand contains additional sulfur- Nitrogen Atoms at
least one additional containing rings that constitute S binding
sites. Sulfur Atom Binding Site in a Separate Can include other
ring systems bound to the N- Ring (N--S Bidentates, N--S
Tridentates, N--S or S-containing heterocyclic rings, but they do
Tetradentates) not coordinate with the stabilized, high valence
metal ion. Ring(s) can also contain O, S, or P atoms. This
5-membered ring(s) and/or additional S-containing ring(s) and/or
attached, uncoordinating rings may or may not have halogen or
polarizing or water- insolubilizing/solubilizing groups attached.
N--S Valence Stabilizer #34: Six membered heterocyclic ring(s)
containing Six-Membered Heterocyclic Rings one, two, three, or four
nitrogen atoms. In containing One, Two, Three, or Four addition,
ligand contains additional sulfur- Nitrogen Atoms at least one
additional containing rings that constitute S binding sites. Sulfur
Atom Binding Site in a Separate Can include other ring systems
bound to the N- Ring (N--S Bidentates, N--S Tridentates, N--S or
S-containing heterocyclic rings, but they do Tetradentates) not
coordinate with the stabilized, high valence metal ion. Ring(s) can
also contain O, S, or P atoms. This 6-membered ring(s) and/or
additional S-containing ring(s) and/or attached, uncoordinating
rings may or may not have halogen or polarizing or water-
insolubilizing/solubilizing groups attached. N--S Valence
Stabilizer #35: Macrocyclic ligands containing two, three, four,
Two-, Three-, Four-, Six-, Eight-, and Ten- six, eight, or ten
binding sites composed of Membered Macrocyclics, Macrobicyclics,
nitrogen and sulfur to valence stabilize the and Macropolycyclics
(including central metal ion. Can include other Catapinands,
Cryptands, Cyclidenes, and hydrocarbon or ring systems bound to
this Sepulchrates) wherein all Binding Sites are macrocyclic
ligand, but they do not coordinate composed of Nitrogen (usually
amine or with the stabilized, high valence metal ion. This imine
groups) or Sulfur (usually thiols, ligand and/or attached,
uncoordinating mercaptans, or thiocarbonyls) and are not
hydrocarbons/rings may or may not have contained in Component
Heterocyclic halogen or polarizing or water- Rings (N--S
Bidentates, N--S Tridentates, N-- insolubilizing/solubilizing
groups attached. S Tetradentates, and N--S Hexadentates) N--S
Valence Stabilizer #36: Macrocyclic ligands containing a total of
four, Four-, Six-, Eight-, or Ten-Membered six, eight, or ten
heterocyclic rings containing Macrocyclics, Macrobicyclics, and
nitrogen or sulfur binding sites. Can include Macropolycyclics
(including Catapinands, other hydrocarbon/ring systems bound to
this Cryptands, Cyclidenes, and Sepulchrates) macrocyclic ligand,
but they do not coordinate wherein all Binding Sites are composed
of with the stabilized, high valence metal ion. This Nitrogen or
Sulfur and are contained in ligand and/or attached, uncoordinating
Component Heterocyclic Rings (N--S hydrocarbon/rings may or may not
have halogen Bidentates, N--S Tridentates, N--S or polarizing or
water-insolubilizing groups Tetradentates, or N--S Hexadentates)
attached. N--S Valence Stabilizer #37: Macrocyclic ligands
containing at least one Four-, Six-, Eight-, or Ten-Membered
heterocyclic ring. These heterocyclic rings Macrocyclics,
Macrobicyclics, and provide nitrogen or sulfur binding sites to
Macropolycyclics (including Catapinands, valence stabilize the
central metal ion. Other Cryptands, Cyclidenes, and Sepulchrates)
amine, imine, thiol, mercapto, or thiocarbonyl wherein all Binding
Sites are composed of binding sites can also be included in the
Nitrogen or Sulfur and are contained in a macrocyclic ligand, so
long as the total number Combination of Heterocyclic Rings and of
binding sites is four, six, eight, or ten. Can Amine, Imine, Thiol,
Mercapto, or include other hydrocarbon/ring systems bound
Thiocarbonyl Groups (N--S Bidentates, N--S to this macrocyclic
ligand, but they do not Tridentates, N--S Tetradentates, or N--S
coordinate with the stabilized, high valence Hexadentates) metal
ion. This ligand and/or attached, uncoordinating hydrocarbon/rings
may or may not have halogen or polarizing or water- insolubilizing
groups attached. N--O Valence Stabilizer #1:
R'--N(--OH)--C(--R).dbd.N--R'', where R, R', and R'' N-Hydroxy(or
N,N'-dihydroxy)amidines represent H or any organic functional group
and N-Hydroxy(or N,N'- wherein the number of carbon atoms ranges
dihydroxy)diamidines (N--O Bidentates, N-- from 0 to 40, optionally
having halogen or O Tridentates, or N--O Tetradentates) polarizing
or water-insolubilizing/solubilizing groups attached. Ligand can
also contain nonbinding N, O, S, or P atoms. N--O Valence
Stabilizer #2: RR'--N--C(.dbd.NH)--NR''--CO--NR'''R'''' for
Guanylureas, Guanidinoureas, guanylureas, and
RR'--N--C(.dbd.NH)--NR''--NH--CO-- Bis(guanylureas),
Bis(guanidinoureas), NR'''R'''' for guanidinoureas, where R, R',
R'', Poly(guanylureas), and R''', and R'''' represent H, NH.sub.2,
or any organic Poly(guanidinoureas) (N--O Bidentates and functional
group wherein the number of carbon N--O Tetradentates) atoms ranges
from 0 to 40, optionally having halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--O Valence Stabilizer #3:
RR'--N--C(.dbd.NH)--NR''--CO--R''' for N-- Amidinoamides,
Guanidinoamides, amidinoamides, or RR'--N--C(.dbd.NH)--CR''R'''--
Bis(amidinoamides), Bis(guanidinoamides), CO--N--R''''R''''' for
2-amidinoacetamides, and Poly(amidinoamides), and
RR'--N--C(.dbd.NH)--NR''--NH--CO--R''' for Poly(guanidinoamides)
(including both N-- guanidinoamides, where R, R', R'', R''', R'''',
amidinoamides and 2-amidinoacetamides) and R''''' represent H,
NH.sub.2, or any organic (N--O Bidentates and N--O Tetradentates)
functional group wherein the number of carbon atoms ranges from 0
to 40, optionally having halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--O Valence Stabilizer #4:
R--C(.dbd.NH)--NR'--CO--R'', where R, R', and R'', Imidoylamides,
Bis(imidoylamides), and represent H or any organic functional group
Poly(imidoylamides) (N--O Bidentates and wherein the number of
carbon atoms ranges N--O Tetradentates) from 0 to 40, optionally
having halogen or polarizing or water-insolubilizing/solubilizing
groups attached. Ligand can also contain nonbinding N, O, S, or P
atoms. N--O Valence Stabilizer #5:
RR'--N--C(.dbd.NH)--O--CO--NR''R''', where R, R',
O-Amidinocarbamates, Bis(O- R'', and R''' represent H, NH.sub.2, or
any organic amidinocarbamates), and Poly(O- functional group
wherein the number of carbon amidinocarbamates) (N--O Bidentates
and atoms ranges from 0 to 40, optionally having N--O
Tetradentates) halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--O Valence Stabilizer #6:
RR'--N--C(.dbd.NH)--S--CO--NR''R''', where R, R',
S-Amidinothiocarbamates, Bis(S- R'', and R''' represent H,
NH.sub.2, or any organic amidinothiocarbamates), and Poly(S-
functional group wherein the number of carbon
amidinothiocarbamates) (N--O Bidentates atoms ranges from 0 to 40,
optionally having and N--O Tetradentates) halogen or polarizing or
water- insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--O Valence Stabilizer #7:
(NH.dbd.)(NH.dbd.)P(OR)(OR'), where R, R', and R'' Diimidosulfuric
Acid, Bis(diimidosulfuric represent H, NH.sub.2, or any organic
functional acid), and derivatives thereof (N--O group wherein the
number of carbon atoms Bidentates and N--O Tetradentates) ranges
from 0 to 40, optionally having halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--O Valence Stabilizer #8:
(NH.dbd.)P(--OR)(--OR')(--OR''), where R, R', and Phosphorimidic
Acid, Bis(phosphorimidic R'' represent H, NH.sub.2, or any organic
functional acid); and Poly(phosphorimidic acid), and group wherein
the number of carbon atoms derivatives thereof (N--O Bidentates)
ranges from 0 to 40, optionally having halogen or polarizing or
water- insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--O Valence Stabilizer #9:
(O.dbd.)P(--NRR')(--NR''R''')(--NR''''R'''''), where R, Phosphoric
Triamides, Bis(phosphoric R', R'', R''', R'''', and R'''''
represent H, NH.sub.2, or triamides), and Poly(phosphoric
triamides) any organic functional group wherein the (N--O
Bidentates and N--O Tetradentates) number of carbon atoms ranges
from 0 to 40, optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--O Valence Stabilizer
#10: (O.dbd.)P(--NRR')(--OR'')(--OR''') for Phosphoramidic Acid,
Phosphorodiamidic phosphoramidic acid and (O.dbd.)P(--NRR')(--
Acid, Bis(phosphoramidic acid), NR''R''')(--OR'''') for
phosphorodiamidic acid, Bis(phosphorodiamidic acid), where R, R',
R'', R''', and R'''' represent H, Poly(phosphoramidic acid),
NH.sub.2, or any organic functional group wherein
Poly(phosphorodiamidic acid), and the number of carbon atoms ranges
from 0 to derivatives thereof (N--O Bidentates and N-- 40,
optionally having halogen or polarizing or O Tetradentates)
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--O Valence Stabilizer
#11: R'--C(.dbd.O)--N.dbd.C(--R)(--NHR''), where R is an N-Acyl
7-Aminobenzylidenimines (N--O aromatic derivative (i.e.,
--C.sub.6H.sub.5), and R' and R'' Bidentates or N--O Tetradentates)
represent H, NH.sub.2, or any organic functional group wherein the
number of carbon atoms ranges from 0 to 40, optionally having
halogen or polarizing or water- insolubilizing/solubilizing groups
attached. Ligand can also contain nonbinding N, O, S, or P atoms.
N--O Valence Stabilizer #12: R--C(.dbd.NOH)--R' for oximes, and
R--C(.dbd.NOH)-- Oximes, Dioximes, and Poly(oximes) (N--O
C(.dbd.NOH)--R' for dioximes, where R and R' Bidentates, N--O
Tridentates, and N--O represent H, NH.sub.2, or any organic
functional Tetradentates) group wherein the number of carbon atoms
ranges from 0 to 40, optionally having halogen or polarizing or
water- insolubilizing/solubilizing groups attached.
Ligand can also contain nonbinding N, O, S, or P atoms. N--O
Valence Stabilizer #13: R--C(.dbd.O)--C(.dbd.NOH)--R', where R and
R' Carbonyl oximes, Bis(carbonyl oximes), represent H, NH.sub.2, or
any organic functional and Poly(carbonyl oximes) (N--O group
wherein the number of carbon atoms Bidentates, N--O Tridentates,
and N--O ranges from 0 to 40, optionally having halogen
Tetradentates) or polarizing or water- insolubilizing/solubilizing
groups attached. Ligand can also contain nonbinding N, O, S, or P
atoms. N--O Valence Stabilizer #14:
R--C(.dbd.N--R'')--C(.dbd.NOH)--R', where R, R', and Imine oximes,
Bis(imine oximes), and R'' represent H, NH.sub.2, or any organic
functional Poly(imine oximes) (including 2-Nitrogen group wherein
the number of carbon atoms heterocyclic oximes) (N--O Bidentates,
N--O ranges from 0 to 40, optionally having halogen Tridentates,
N--O Tetradentates, and N--O or polarizing or water- Hexadentates)
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--O Valence Stabilizer
#15: R--CH(--OH)--C(.dbd.NOH)--R', where R, R', and R'' Hydroxy
oximes, Bis(hydroxy oximes), and represent H, NH.sub.2, or any
organic functional Poly(hydroxy oximes) (including 2-Oxygen group
wherein the number of carbon atoms heterocyclic oximes) (N--O
Bidentates, N--O ranges from 0 to 40, optionally having halogen
Tridentates, N--O Tetradentates, and N--O or polarizing or water-
Hexadentates) insolubilizing/solubilizing groups attached. Ligand
can also contain nonbinding N, O, S, or P atoms. N--O Valence
Stabilizer #16: RR'--C(--NH--R'')--C(.dbd.NOH)--R''', where R, R',
Amino oximes, Bis(amino oximes), and R'', and R''' represent H,
NH.sub.2, or any organic Poly(amino oximes) (N--O Bidentates, N--O
functional group wherein the number of carbon Tridentates, N--O
Tetradentates, and N--O atoms ranges from 0 to 40, optionally
having Hexadentates) halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--O Valence Stabilizer
#17: RR'--N--C(.dbd.NOH)--R'', where R, R', and R'' Amido oximes,
Bis(amido oximes), and represent H, NH.sub.2, or any organic
functional Poly(amido oximes) (N--O Bidentates, N--O group wherein
the number of carbon atoms Tridentates, N--O Tetradentates, and
N--O ranges from 0 to 40, optionally having halogen Hexadentates)
or polarizing or water- insolubilizing/solubilizing groups
attached. Ligand can also contain nonbinding N, O, S, or P atoms.
N--O Valence Stabilizer #18: R--N.dbd.N--C(.dbd.NOH)--R' or
RR'C.dbd.N--NR''-- Azo oximes, Bis(azo oximes), and Poly(azo
C(.dbd.NOH)--R''', where R, R', R'', and R''' oximes) (N--O
Bidentates, N--O Tridentates, represent H, NH.sub.2, or any organic
functional N--O Tetradentates, and N--O Hexadentates). group
wherein the number of carbon atoms Also includes hydrazone oximes.
ranges from 0 to 40, optionally having halogen or polarizing or
water- insolubilizing/solubilizing groups attached. (R is typically
an aryl group.) Ligand can also contain nonbinding N, O, S, or P
atoms. N--O Valence Stabilizer #19: o-(ON--)(HO--)Ar, where Ar
represents an 2-Nitrosophenols (o-Quinone monoximes) aromatic group
or heterocyclic wherein the (N--O Bidentates) number of carbon
atoms ranges from 6 to 40, optionally having halogen or polarizing
or water-insolubilizing/solubilizing groups attached. Ligand can
also contain nonbinding N, O, S, or P atoms. N--O Valence
Stabilizer #20: o-(O.sub.2N--)(HO--)Ar, where Ar represents an
2-Nitrophenols (N--O Bidentates) aromatic group or heterocyclic
wherein the number of carbon atoms ranges from 6 to 40, optionally
having halogen or polarizing or water-insolubilizing/solubilizing
groups attached. Ligand can also contain nonbinding N, O, S, or P
atoms. N--O Valence Stabilizer #21: R--C(.dbd.O)--NR'--OH or
R--C(--OH).dbd.N--OH, where Hydroxamates (Hydroxylamines), R and R'
represent H, NH.sub.2, or any organic Bis(hydroxamates), and
functional group wherein the number of carbon Poly(hydroxamates)
(N--O Bidentates, N--O atoms ranges from 0 to 40, optionally having
Tetradentates, and N--O Hexadentates) halogen or polarizing or
water- insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--O Valence Stabilizer
#22: R--N(--NO)--OH, where R represents any organic
N-Nitrosohydroxylamines, Bis(N- functional group wherein the number
of carbon nitrosohydroxylamines), and Poly(N- atoms ranges from 1
to 40, optionally having nitrosohydroxylamines) (N--O Bidentates,
halogen or polarizing or water- N--O Tetradentates, and N--O
Hexadentates) insolubilizing/solubilizing groups attached. (R is
typically an aryl or heterocyclic group.) Ligand can also contain
nonbinding N, O, S, or P atoms. N--O Valence Stabilizer #23:
R--CH(--NHR')--C(.dbd.O)(--OH) for amino acids and Amino Acids and
ortho-Aminocarboxylic ortho-aminocarboxylic acids, and R--CH(--
Acids, Peptides, Polypeptides, and Proteins
NHR')--C(.dbd.O)--(NR''--)CH(--R''')--C(.dbd.O)(--OH) [N--O
Bidentates, N--O Tridentates, and N--O for peptides, where R, R',
R'', and R''' represent Tetradentates; possibly S--O dentates for
any organic functional group wherein the sulfur-contg. examples
such as number of carbon atoms ranges from 1 to 40, penicillamine
and cystine] optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--O Valence Stabilizer
#24: RCONR'R'', where R, R', and R'' represent H, Amides,
Bis(amides), and Poly(amides), NH.sub.2, or any organic functional
group wherein including lactams (N--O Bidentates, N--O the number
of carbon atoms ranges from 0 to Tridentates, and N--O
Tetradentates) 40, optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--O Valence Stabilizer
#25: RR'--N--C(.dbd.O)--NR''--N.dbd.CR'''R'''', where R, R',
Semicarbazones, Bis(semicarbazones), and R'', R''', and R''''
represent H, or any organic Poly(semicarbazones) (N--O Bidentates,
N-- functional group wherein the number of carbon O Tetradentates,
and N--O Hexadentates) atoms ranges from 0 to 40, optionally having
halogen or polarizing or water- insolubilizing/solubilizing groups
attached. Ligand can also contain nonbinding N, O, S, or P atoms.
N--O Valence Stabilizer #26: R--C(.dbd.O)--NR'--N.dbd.CR''R''',
where R, R', R'', and Acyl hydrazones, Bis(acyl hydrazones), and
R''' represent H, or any organic functional Poly(acyl hydrazones)
(N--O Bidentates, N-- group wherein the number of carbon atoms O
Tetradentates, and N--O Hexadentates) ranges from 0 to 40,
optionally having halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--O Valence Stabilizer
#27: R--N.dbd.N--C(.dbd.O)--NR'--N--R''R''', where R, R', R'',
Carbazones (Diazenecarboxylic and R''' represent H, or any organic
functional hydrazides), Bis(carbazones), and group wherein the
number of carbon atoms Poly(carbazones) (N--O Bidentates, N--O
ranges from 0 to 40, optionally having halogen Tetradentates, and
N--O Hexadentates) or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--O Valence Stabilizer
#28: R--N.dbd.N--R', where R, and R' represent H or any Azo
compounds with hydroxyl or carboxy organic functional group wherein
the number of or carbonyl substitution at the ortho- (for carbon
atoms ranges from 0 to 40, optionally aryl) or alpha- or beta- (for
alkyl) positions, having halogen or polarizing or water-
Bis[o-(HO--) or alpha- or beta-(HO--)azo
insolubilizing/solubilizing groups attached. compounds], or
Poly[o-(HO--) or alpha- or (Must include ortho-hydroxy or carboxy
or beta-(HO--)azo compounds) (N--O carbonyl substituted aryl azo
compounds, and Bidentates, N--O Tridentates, N--O alpha- or
beta-hydroxy or carboxy or carbonyl Tetradentates, or N--O
Hexadentates) alkyl azo compounds.) Ligand can also contain
nonbinding N, O, S, or P atoms. N--O Valence Stabilizer #29:
R--N.dbd.N--C(.dbd.O)--NR'R'' for diazeneformamides,
Diazeneformamides, Diazeneacetamides, and
R--N.dbd.N--CR'R''--C(.dbd.O)--NR'''R'''' for
Bis(diazeneformamides), diazeneacetamides, where R, R', R'', R''',
and Bis(diazeneacetamides), R'''' represent H, NH.sub.2, or any
organic functional Poly(diazeneformamides), and group wherein the
number of carbon atoms Poly(diazeneacetamides) (N--O Bidentates,
ranges from 0 to 40, optionally having halogen N--O Tetradentates,
and N--O Hexadentates) or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--O Valence Stabilizer
#30: R--N.dbd.N--C(.dbd.O)--O--R' for diazeneformic acid,
Diazeneformic acids, Diazeneacetic acids, and
R--N.dbd.N--CR'R''--C(.dbd.O)--O--R''' for Bis(diazeneformic
acids), Bis(diazeneacetic diazeneacetic acid, where R, R', R'', and
R''' acids), Poly(diazeneformic acids), represent H, NH.sub.2, or
any organic functional Poly(diazeneacetic acids), and derivatives
group wherein the number of carbon atoms thereof (N--O Bidentates,
N--O ranges from 0 to 40, optionally having halogen Tetradentates,
N--O Hexadentates) or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--O Valence Stabilizer
#31: R--N.dbd.N--C(.dbd.O)--R' for diazenefornialdehydes,
Diazeneformaldehydes, and R--N.dbd.N--CR'R''--C(.dbd.O)--R''' for
Diazeneacetaldehydes, diazeneacetaldehydes, where R, R', R'', and
R''' Bis(diazeneformaldehydes), represent H, NH.sub.2, or any
organic functional Bis(diazeneacetaldehydes), group wherein the
number of carbon atoms Poly(diazeneformaldehydes), and ranges from
0 to 40, optionally having halogen Poly(diazeneacetaldehydes) (N--O
or polarizing or water- Bidentates, N--O Tetradentates and N--O
insolubilizing/solubilizing groups attached. Hexadentates) Ligand
can also contain nonbinding N, O, S, or P atoms. N--O Valence
Stabilizer #32: RR'--N--C(.dbd.O)--N.dbd.N--C(.dbd.O)--NR''R''' for
Diazenediformamides, diazenediformamides, and RR'--N--C(.dbd.O)--
Diazenediacetamides,
CR''R'''--N.dbd.N--CR''''R'''''--C(.dbd.O)--NR''''''R- '''''''
Bis(diazenediformamides), for diazenediacetamides, where R, R',
R'', R''', Bis(diazenediacetamides), R'''', R''''', R'''''', and
R''''''' represent H, NH.sub.2, Poly(diazenediformamides), and or
any organic functional group wherein the
Poly(diazenediacetamides) (N--O number of carbon atoms ranges from
0 to 40, Tridentates and N--O Hexadentates) optionally having
halogen or polarizing or water-insolubilizing/solubilizing groups
attached. Ligand can also contain nonbinding N, O, S, or P atoms.
N--O Valence Stabilizer #33:
R--O--C(.dbd.O)--N.dbd.N--C(.dbd.O)--O--R' for Diazenediformic
acids, Diazenediacetic diazenediformic acid, and
R--O--C(.dbd.O)--CR'R''-- acids, Bis(diazenediformic acids),
N.dbd.N--CR'''R''''--C(.dbd.O)--O--R''''' for Bis(diazenediacetic
acids), diazenediacetic acid, where R, R', R'', R''', R'''',
Poly(diazenediformic acids), and R''''' represent H, NH.sub.2, or
any organic Poly(diazenediacetic acids) and derivatives functional
group wherein the number of carbon thereof (N--O Tridentates and
N--O atoms ranges from 0 to 40, optionally having Hexadentates)
halogen or polarizing or water- insolubilizing/solubilizing groups
attached. Ligand can also contain nonbinding N, O, S, or P atoms.
N--O Valence Stabilizer #34: RC(.dbd.O)--N.dbd.N--C(.dbd.O)--R' for
Diazenediformaldehydes, diazenediformaldehydes, and
RC(.dbd.O)--CR'R''-- Diazenediacetaldehydes,
N.dbd.N--CR'''R''''--C(.dbd.O)--R''''' for
Bis(diazenediformaldehydes), diazenediacetaldehydes, where R, R',
R'', R''', Bis(diazenediacetaldehydes), R'''', and R''''' represent
H, NH.sub.2, or any organic Poly(diazenediformaldehydes), and
functional group wherein the number of carbon
Poly(diazenediacetaldehydes) (N--O atoms ranges from 0 to 40,
optionally having Tridentates and N--O Hexadentates) halogen or
polarizing or water- insolubilizing/solubilizing groups attached.
Ligand can also contain nonbinding N, O, S, or P atoms. N--O
Valence Stabilizer #35: R--N.dbd.N--CR'.dbd.N--NR''R''', where R,
R', R'', and Ortho-hydroxy (or -carboxy) Substituted R''' represent
H, or any organic functional Formazans, Bis(o-hydroxy or -carboxy
group wherein the number of carbon atoms substituted formazans),
and Poly(o-hydroxy ranges from 0 to 40, optionally having halogen
or -carboxy substituted formazans) (N--O or polarizing or water-
Bidentates, N--O Tridentates, N--O insolubilizing/solubilizing
groups attached. Tetradentates, and N--O Hexadentates) (Must
include ortho-hydroxy or carboxy substituted aryl R derivatives,
and beta-hydroxy or carboxy substituted alkyl R derivatives.)
Ligand can also contain nonbinding N, O, S, or P atoms. N--O
Valence Stabilizer #36: RR'C.dbd.N--N.dbd.CR''R''' or
RR'C.dbd.N--NR''R''' (for Ortho-hydroxy (or -carboxy) Substituted
ketazines), where R, R', R'', and R''' represent Azines (including
ketazines), Bis(o- H, or any organic functional group wherein the
hydroxy or carboxy substituted azines), and number of carbon atoms
ranges from 0 to 40, Poly(o-hydroxy or carboxy substituted
optionally having halogen or polarizing or azines) (N--O
Bidentates, N--O Tridentates, water-insolubilizing/solubilizing
groups N--O Tetradentates, and N--O Hexadentates) attached. (Must
include ortho-hydroxy or carboxy substituted aryl R derivatives,
and beta- hydroxy or carboxy substituted alkyl R derivatives.)
Ligand can also contain nonbinding N, O, S, or P atoms. N--O
Valence Stabilizer #37: RR'C.dbd.N--R'', where R, R', and R''
represent H, Schiff Bases with one Imine (C.dbd.N) Group or any
organic functional group wherein the and with ortho- or alpha- or
beta-hydroxy number of carbon atoms ranges from 0 to 40, or carboxy
or carbonyl substitution (N--O optionally having halogen or
polarizing or Bidentates, N--O Tridentates, N--O
water-insolubilizing/solubilizing groups Tetradentates, N--O
Pentadentates, or N--O attached. (Must contain ortho- or alpha- or
beta- Hexadentates). Also includes hydrazones hydroxy or carboxy or
carbonyl substitution.) with ortho-O substitution. Ligand can also
contain nonbinding N, O, S, or P atoms. N--O Valence Stabilizer
#38: RR'C.dbd.N--R''--N.dbd.CR'''R'''' or R--N.dbd.C--R'--C.dbd.N--
Schiff Bases with two Imine (C.dbd.N) Groups R' or
RC.dbd.N--R'--N.dbd.CR'', where R, R', R'', R''', and with ortho-
or alpha- or beta-hydroxy and R'''' represent H, or any organic
functional or carboxy or carbonyl substitution (N--O group wherein
the number of carbon atoms Tridentates, N--O Tetradentates, N--O
ranges from 0 to 40, optionally having halogen Pentadentates, or
N--O Hexadentates). Also or polarizing or water- includes
hydrazones with ortho-O insolubilizing/solubilizing groups
attached. substitution. (Must contain ortho- or alpha- or
beta-hydroxy or carboxy or carbonyl substitution.) Ligand can also
contain nonbinding N, O, S, or P atoms. N--O Valence Stabilizer
#39: N(--R--N.dbd.CR'R'').sub.3, where R, R', and R'' Schiff Bases
with three Imine (C.dbd.N) represent H, or any organic functional
group Groups and with ortho- or alpha- or beta- wherein the number
of carbon atoms ranges hydroxy or carboxy or carbonyl substitution
from 0 to 40, optionally having halogen or (N--O Tetradentates,
N--O Pentadentates, or polarizing or
water-insolubilizing/solubilizing N--O Hexadentates). Also includes
groups attached. (Must contain ortho- or alpha- hydrazones with
ortho-O substitution. or beta-hydroxy or carboxy or carbonyl
substitution.) Ligand can also contain nonbinding N, O, S, or P
atoms. N--O Valence Stabilizer #40:
[R--C(NR'R'')].sub.x--R''--[Si(--OR''').sub.zR''''.sub.3-z].sub.y
where Silylaminoalcohols (N--O Bidentates, N--O R, R', R'', R''',
and R'''' represent H, NH.sub.2, or Tridentates, N--O
Tetradentates, and N--O any organic functional group wherein the
Hexadentates) number of carbon atoms ranges from 0 to 40,
optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached, and x and y =
1-6, z = 1-3. Ligand can also contain nonbinding N, O, S, or P
atoms. N--O Valence Stabilizer #41:
[R--C(.dbd.NR')].sub.x--R''--[C(--OR''')R''''R'''''].sub.y or [R--
Hydroxyalkyl Imines (Imino Alcohols) (N--
C(.dbd.NR')].sub.x--R''--[C(.dbd.O)R'''].sub.y, where R, R', R'', O
Bidentates, N--O Tridentates, N--O R''', R'''', and R'''''
represent H, NH.sub.2, or any Tetradentates, and N--O Hexadentates)
organic functional group wherein the number of carbon atoms ranges
from 0 to 40, optionally having halogen or polarizing or water-
insolubilizing/solubilizing groups attached, and x and y = 1-6.
Ligand can also contain nonbinding N, O, S, or P atoms. N--O
Valence Stabilizer #42: [R(--NR'R'')(--OR''')],
[R(--NR'R'')(--C(.dbd.O)R'''], Hydroxyaryl Amines and Hydroxyaryl
[R(--NR'R'').sub.x].sub.2O,
[R(--NR'R'').sub.x].sub.2-.sub.3R'''(--OR'''').sub.y, Imines (N--O
Bidentates, N--O Tridentates,
[R(--OR').sub.x].sub.2-.sub.3R''(--NR'''R'''').sub.y, and [R(--
N--O Tetradentates, and N--O Hexadentates)
NR'R'').sub.x].sub.2R'''(C(.dbd.O)).sub.yR'''' for hydroxyaryl
amines; and [R(--OR').sub.x].sub.2NH or [R(-- OR').sub.x].sub.2NHNH
for hydroxyaryl imines, where R, R', R'', R''', and R'''' represent
H, NH.sub.2, or any organic functional group wherein the number of
carbon atoms ranges from 0 to 40, optionally having halogen or
polarizing or water-insolubilizing/solubilizing groups attached,
and x = 0-2 and y = 1-4. Ligand can also contain nonbinding N, O,
S, or P atoms. N--O Valence Stabilizer #43: Five membered
heterocyclic ring(s) containing Five-Membered Heterocyclic Rings
one, two, three, or four nitrogen atoms. In containing One, Two,
Three, or Four addition, ligand contains additional oxygen-
Nitrogen Atoms with at least one additional containing substituents
(usually hydroxy, Oxygen Atom Binding Site not in a Ring carboxy or
carbonyl groups) that constitute O (N--O Bidentates, N--O
Tridentates, N--O binding sites. Can include other ring systems
Tetradentates, or N--O Hexadentates) bound to the heterocyclic ring
or to the O- containing substituent, but they do not coordinate
with the stabilized, high valence metal ion. Ring(s) can also
contain O, S, or P atoms. This 5-membered ring(s) and/or attached,
uncoordinating rings and/or O- containing substituent(s) may or may
not have halogen or polarizing or water-
insolubilizing/solubilizing groups attached. N--O Valence
Stabilizer #44: Six membered heterocyclic ring(s) containing
Six-Membered Heterocyclic Rings one, two, three, or four nitrogen
atoms. In containing One, Two, Three, or Four addition, ligand
contains additional oxygen- Nitrogen Atoms with at least one
additional containing substituents (usually hydroxy, Oxygen Atom
Binding Site not in a Ring carboxy, or carbonyl groups) that
constitute O (N--O Bidentates, N--O Tridentates, N--O binding
sites. Can include other ring systems Tetradentates, or N--O
Hexadentates) bound to the heterocyclic ring or to the O-
containing substituent, but they do not coordinate with the
stabilized, high valence metal ion. Ring(s) can also contain O, S,
or P atoms. This 6-membered ring(s) and/or attached, uncoordinating
rings and/or O- containing substiruent(s) may or may not have
halogen or polarizing or water- insolubilizing/solubilizing groups
attached. N--O Valence Stabilizer #45: Five membered heterocyclic
ring(s) containing Five-Membered Heterocyclic Rings one or two
oxygen atoms. In addition, ligand containing One or Two Oxygen
Atoms with contains additional nitrogen-containing at least one
additional Nitrogen Atom substituents (usually amines, imines, or
Binding Site not in a Ring (N--O Bidentates, hydrazides) that
constitute N binding sites. Can N--O Tridentates, N--O
Tetradentates, or N-- include other ring systems bound to the O
Hexadentates) heterocyclic ring or to the N-containing substituent,
but they do not coordinate with the stabilized, high valence metal
ion. Ring(s) can also contain O, S, or P atoms. This 5-membered
ring(s) and/or attached, uncoordinating rings and/or N-containing
substituent(s) may or may not have halogen or polarizing or water-
insolubilizing/solubilizing groups attached. N--O Valence
Stabilizer #46: Six membered heterocyclic ring(s) containing
Six-Membered Heterocyclic Rings one or two oxygen atoms. In
addition, ligand containing One or Two Oxygen Atoms with contains
additional nitrogen-containing at least one additional Nitrogen
Atom substituents (usually amines, imines, or Binding Site not in a
Ring (N--O Bidentates, hydrazides) that constitute N binding sites.
Can N--O Tridentates, N--O Tetradentates, or N-- include other ring
systems bound to the O Hexadentates) heterocyclic ring or to the
N-containing substituent, but they do not coordinate with the
stabilized, high valence metal ion. Ring(s) can also contain O, S,
or P atoms. This 6-membered ring(s) and/or attached, uncoordinating
rings and/or N-containing substituent(s) may or may not have
halogen or polarizing or water- insolubilizing/solubilizing groups
attached. N--O Valence Stabilizer #47: Five membered heterocyclic
ring(s)
containing Five-Membered Heterocyclic Rings one, two, three, or
four nitrogen atoms. In containing One, Two, Three, or Four
addition, ligand contains additional oxygen- Nitrogen Atoms with at
least one additional containing rings that constitute O binding
sites. Oxygen Atom Binding Site in a Separate Can include other
ring systems bound to the N- Ring (N--O Bidentates, N--O
Tridentates, N-- or O-containing heterocyclic rings, but they do O
Tetradentates) not coordinate with the stabilized, high valence
metal ion. Ring(s) can also contain O, S, or P atoms. This
5-membered ring(s) and/or additional O-containing ring(s) and/or
attached, uncoordinating rings may or may not have halogen or
polarizing or water- insolubilizing/solubilizing groups attached.
N--O Valence Stabilizer #48: Six membered heterocyclic ring(s)
containing Six-Membered Heterocyclic Rings one, two, three, or four
nitrogen atoms. In containing One, Two, Three, or Four addition,
ligand contains additional oxygen- Nitrogen Atoms with at least one
additional containing rings that constitute O binding sites. Oxygen
Atom Binding Site in a Separate Can include other ring systems
bound to the N- Ring (N--O Bidentates, N--O Tridentates, N-- or
O-containing heterocyclic rings, but they do O Tetradentates) not
coordinate with the stabilized, high valence metal ion. Ring(s) can
also contain O, S, or P atoms. This 6-membered ring(s) and/or
additional O-containing ring(s) and/or attached, uncoordinating
rings may or may not have halogen or polarizing or water-
insolubilizing/solubilizing groups attached. N--O Valence
Stabilizer #49: Macrocyclic ligands containing two, three, four,
Two-, Three-, Four-, Six-, Eight-, and Ten- six, eight, or ten
binding sites composed of Membered Macrocyclics, Macrobicyclics,
nitrogen and oxygen to valence stabilize the and Macropolycyclics
(including central metal ion. Can include other Catapinands,
Cryptands, Cyclidenes, and hydrocarbon or ring systems bound to
this Sepulchrates) wherein all Binding Sites are macrocyclic
ligand, but they do not coordinate composed of Nitrogen (usually
amine or with the stabilized, high valence metal ion. This imine
groups) or Oxygen (usually hydroxy, ligand and/or attached,
uncoordinating carboxy, or carbonyl groupss) and are not
hydrocarbons/rings may or may not have contained in Component
Heterocyclic halogen or polarizing or water- Rings (N--O
Bidentates, N--O Tridentates, insolubilizing/solubilizing groups
attached. N--O Tetradentates, and N--O Hexadentates) N--O Valence
Stabilizer #50: Macrocyclic ligands containing a total of four,
Four-, Six-, Eight-, or Ten-Membered six, eight, or ten
heterocyclic rings containing Macrocyclics, Macrobicyclics, and
nitrogen or oxygen binding sites. Can include Macropolycyclics
(including Catapinands, other hydrocarbon/ring systems bound to
this Cryptands, Cyclidenes, and Sepulchrates) macrocyclic ligand,
but they do not coordinate wherein all Binding Sites are composed
of with the stabilized, high valence metal ion. This Nitrogen or
Oxygen and are contained in ligand and/or attached, uncoordinating
Component Heterocyclic Rings (N--O hydrocarbon/rings may or may not
have halogen Bidentates, N--O Tridentates, N--O or polarizing or
water-insolubilizing groups Tetradentates, or N--O Hexadentates)
attached. N--O Valence Stabilizer #51: Macrocyclic ligands
containing at least one Four-, Six-, Eight-, or Ten-Membered
heterocyclic ring. These heterocyclic rings Macrocyclics,
Macrobicyclics, and provide nitrogen or oxygen binding sites to
Macropolycyclics (including Catapinands, valence stabilize the
central metal ion. Other Cryptands, Cyclidenes, and Sepulchrates)
amine, imine, hydroxy, carboxy, or carbonyl wherein all Binding
Sites are composed of binding sites can also be included in the
Nitrogen or Oxygen and are contained in a macrocyclic ligand, so
long as the total number Combination of Heterocyclic Rings and of
binding sites is four, six, eight, or ten. Can Amine, Imine,
Hydroxy, Carboxy, or include other hydrocarbon/ring systems bound
Carbonyl Groups (N--O Bidentates, N--O to this macrocyclic ligand,
but they do not Tridentates, N--O Tetradentates, or N--O coordinate
with the stabilized, high valence Hexadentates) metal ion. This
ligand and/or attached, uncoordinating hydrocarbon/rings may or may
not have halogen or polarizing or water- insolubilizing groups
attached. S--O Valence Stabilizer #1:
R--C(.dbd.S)--CR'R''--C(.dbd.O)--R''' where R, R', R'',
1,3-Monothioketones (Monothio-beta- and R''' represent H, NH.sub.2,
or any organic ketonates), 1,3,5-Monothioketones, 1,3,5- functional
group wherein the number of carbon Dithioketones,
Bis(1,3-Monothioketones), atoms ranges from 0 to 40, optionally
having and Poly(1,3-Monothioketones) (S--O halogen or polarizing or
water- Bidentates, S--O Tridentates, S--O
insolubilizing/solubilizing groups attached. Tetradentates) Ligand
can also contain nonbinding N, O, S, or P atoms. S--O Valence
Stabilizer #2:
RR'--N--C(.dbd.S)--CR''R'''--C(.dbd.O)--N--R''''R'''''
Thiomalonamides (Thiomalonodiamides), where R, R', R'', R''',
R'''', and R''''' represent H, Bis(thiomalonamides), and NH.sub.2,
or any organic functional group wherein Polythiomalonamides (S--O
Bidentates, S--O the number of carbon atoms ranges from 0 to
Tridentates, S--O Tetradentates) 40, optionally having halogen or
polarizing or water-insolubilizing/solubilizing groups attached.
Ligand can also contain nonbinding N, O, S, or P atoms. S--O
Valence Stabilizer #3:
RR'--N--C(.dbd.O)--CR''R'''--C(.dbd.S)--R'''' for 2-
2-Thioacylacetamides, 2- thioacylacetamides, and
RR'--N--C(.dbd.S)--CR''R'''-- Acylthioacetamides, Bis(2-
C(.dbd.O)--R'''' for 2-acylthioacetamides, where R,
thioacylacetamides), R', R'', R''', and R'''' represent H,
NH.sub.2, or any Bis(2acylthioacetamides), Poly(2- organic
functional group wherein the number of thioacylacetamides), and
Poly(2- carbon atoms ranges from 0 to 40, optionally
Acylthioacetamides) (S--O Bidentates, S--O having halogen or
polarizing or water- Tridentates, S--O Tetradentates)
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S--O Valence Stabilizer #4:
RR'--N--C(.dbd.S)--S--C(.dbd.O)--N--R''R''' where R, R',
Dithiodicarbonic Diamides, R'', and R''' represent H, NH.sub.2 or
any organic Bis(dithiodicarbonic diamides), and functional group
wherein the number of carbon Poly(dithiodicarbonic diamides) (S--O
atoms ranges from 0 to 40, optionally having Bidentates, S--O
Tridentates, S--O halogen or polarizing or water- Tetradentates)
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S--O Valence Stabilizer #5:
(R--O--)(R'--O--)P(.dbd.S)--P(.dbd.O)(--O--R'')(--O--R''');
Monothiohypophosphoric Acids,
(R--O--)(R'--S--)P(.dbd.S)--P(O)(--S--R'')(--O--R'''); or
Bis(monothiohypophosphoric acids), and
(R--S--)(R'--S--)P(.dbd.S)--P(.dbd.O)(--S--R'')(--S--R'''),
Poly(monothiohypophosphoric acids), and where R, R', R'', and R'''
represent H, NH.sub.2 or derivatives thereof (S--O Bidentates, S--O
any organic functional group wherein the Tridentates, S--O
Tetradentates) number of carbon atoms ranges from 0 to 40,
optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. Note: these ligands are not
to be confused with hypophosphorous acid derivatives
(hypophosphites) (R--O-- )R''R'''P(.dbd.O) which are very reducing
and therefore unacceptable for stabilization of high valence states
in metal ions. S--O Valence Stabilizer #6:
(RR'--N--)(R''R'''--N--)P(.dbd.S)--P(.dbd.O)(--N--
Monothiohypophosphoramides, R''''R''''')(--N--R''''''R'''''''),
where R, R', R'', R''', Bis(monothiohypophosphoramides), and R'''',
R''''', R'''''', and R''''''' represent H, NH.sub.2 or
Poly(monothiohypophosphoramides) (S--O any organic functional group
wherein the Bidentates, S--O Tridentates, S--O number of carbon
atoms ranges from 0 to 40, Tetradentates) optionally having halogen
or polarizing or water-insolubilizing/solubilizing groups attached.
Ligand can also contain nonbinding N, O, S, or P atoms. Note: these
ligands are not to be confused with hypophosphorous acid
derivatives (hypophosphites) (R--O-- )R''R'''P(.dbd.O) which are
very reducing and therefore unacceptable for stabilization of high
valence states in metal ions. S--O Valence Stabilizer #7:
(R--O--)(R'--O--)P(.dbd.S)--NH--P(.dbd.O)(--O--R'')(--O--
Monothioimidodiphosphoric Acids, R''');
(R--O--)(R'--S--)P(.dbd.S)--NH--P(.dbd.O)(--S--R'')(--
Monothiohydrazidodiphosphoric Acids, O--R'''); or
(R--S--)(R'--S--)P(.dbd.S)--NH--P(.dbd.O)(--S--
Bis(monothioimidodiphosphoric Acids), R'')(--S--R''') for
monothioimidodiphosphoric Bis(monothiohydrazidodiphosphoric acids,
and --NH--NH-- derivatives for Acids),
Poly(monothioimidodiphosphoric monothiohydrazidodiphosphoric acids,
where Acid), R, R', R'', and R''' represent H, NH.sub.2 or any
Poly(monothiohydrazidodiphosphoric organic functional group wherein
the number of Acids), and derivatives thereof (S--O carbon atoms
ranges from 0 to 40, optionally Bidentates, S--O Tridentates, S--O
having halogen or polarizing or water- Tetradentates)
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S--O Valence Stabilizer #8:
(RR'--N--)(R''R'''--N--)P(.dbd.S)--NH--P(.dbd.O)(--N--
Monothioimidodiphosphoramides, R''''R''''')(--N--R''''''R''''''')
for Monothiohydrazidodiphosphoramides,
monothioimidodiphosphoramides, and --NH--
Bis(monothioimidodiphosphoramides), NH-- derivatives for
Bis(monothiohydrazidodiphosphoramides),
monothiohydrazidodiphosphoramides, where R,
Poly(monothioimidodiphosphoramides), R', R'', R''', R'''', R''''',
R'''''', and R''''''' and represent H, NH.sub.2 or any organic
functional Poly(monothiohydrazidodiphosphoramides) group wherein
the number of carbon atoms (S--O Bidentates, S--O Tridentates, S--O
ranges from 0 to 40, optionally having halogen Tetradentates) or
polarizing or water- insolubilizing/solubilizing groups attached.
Ligand can also contain nonbinding N, O, S, or P atoms. S--O
Valence Stabilizer #9:
(RR'--N--)(R''R'''--N--)P(.dbd.S)--S--P(.dbd.O)(--N--
Monothiodiphosphoramides, R''''R''''')(--N--R''''''R'''''''), or
(RR'--N--)(R''R'''-- Bis(monothioiphosphoramides), and
N--)P(.dbd.S)--O--P(.dbd.O)(--N--R''''R''''')(--N--
Poly(monothiodiphosphoramides) (S--O R''''''R'''''''), where R, R',
R'', R''', R'''', R''''', Bidentates, S--O Tridentates, S--O
R'''''', and R''''''' represent H, NH.sub.2 or any Tetradentates)
organic functional group wherein the number of carbon atoms ranges
from 0 to 40, optionally having halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or
P atoms. S--O Valence Stabilizer #10:
(R--O--)(R'--O--)P(.dbd.S)--O--P(.dbd.O)(--O--R'')(--O--R''');
Monothiodiphosphoric Acids,
(R--O--)(R'--O--)P(.dbd.S)--S--P(.dbd.O)(--O--R'')(--O--R''');
Bis(monothioiphosphoric Acids),
(R--O--)(R'--S--)P(.dbd.S)--O--P(.dbd.O)(--S--R'')(--O--R''');
Poly(monothiodiphosphoric Acids), and
(R--O--)(R'--S--)P(.dbd.S)--S--P(.dbd.O)(--S--R'')(--O--R''');
derivatives thereof (S--O Bidentates, S--O or
(R--S--)(R'--S--)P(.dbd.S)--S--P(.dbd.O)(--S--R'')(--S--R'''),
Tridentates, S--O Tetradentates) where R, R', R'', R''', R'''',
R''''', R'''''', and R''''''' represent H, NH.sub.2 or any organic
functional group wherein the number of carbon atoms ranges from 0
to 40, optionally having halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S--O Valence Stabilizer
#11: RR'N.sup.+.dbd.C(OH)(SH), where R and R' represent
Monothiocarbamates, H, OH, SH, OR'' (R''.dbd.C.sub.1-C.sub.30 alkyl
or aryl), SR'' Bis(monothiocarbamates), and
(R''.dbd.C.sub.1-C.sub.30 alkyl or aryl), NH.sub.2 or any organic
Poly(monothiocarbamates) (including N- functional group wherein the
number of carbon hydroxymonothiocarbamates and N- atoms ranges from
0 to 40, optionally having mercaptomonothiocarbamates) (S--O
halogen or polarizing or water- Bidentates, S--O Tridentates, and
S--O insolubilizing/solubilizing groups attached. Tetradentates)
Ligand can also contain nonbinding N, O, S, or P atoms.
N Valence Stabilizer #1: Examples of monoamines (N monodentates)
that meet the requirements for use as "wide band" valence
stabilizers for Co.sup.+3 include, but are not limited to: ammonia,
ethylamine, n-dodecylamine, octylamine, phenylamine,
cyclohexylamine, diethylamine, dioctylamine, diphenylamine,
dicyclohexylamine, azetidine, hexamethylenetetramine, aziridine,
azepine, pyrrolidine, benzopyrrolidine, dibenzopyrrolidine,
naphthopyrrolidine, piperidine, benzopiperidine, dibenzopiperidine,
naphthopiperidine, azacycloheptane (hexamethyleneimine
(Urotropin)), aminonorbornane, adamantanamine, aniline,
benzylamine, toluidine, phenethylamine, xylidine, cumidine,
naphthylamine, polyalkylamines, polyanilines, and fluorenediamine.
N Valence Stabilizer #2: Examples of diamines (N--N bidentates)
that meet the requirements for use as "wide band" valence
stabilizers for Co.sup.+3 include, but are not limited to:
hydrazine, phenylhydrazine, 1,1-diphenylhydrazine,
1,2-diphenylhydrazine (hydrazobenzene), methanediamine,
ethylenediamine (1,2-ethanediamine, en), trimethylenediamine
(1,3-propanediamine), putrescine (1,4-butanediamine), cadaverine
(1,5-pentanediamine), hexamethylenediamine (1,6-hexanediamine),
2,3-diaminobutane, stilbenediamine
(1,2-diphenyl-1,2-ethanediamine), cyclohexane-1,2-diamine,
cyclopentane-1,2-diamine, 1,3-diazacyclopentane,
1,3-diazacyclohexane, piperazine, benzopiperazine,
dibenzopiperazine, naphthopiperazine, diazepine, thiadiazepine,
oxodiazepine, sparteine (lupinidine),
2-(aminomethyl)azacyclohexane, 2-(aminomethyl)piperidine,
2-(aminomethyl)pyrrolidine, 2-(aminomethyl)azetidine,
2-(2-aminoethyl)aziridine, 1,2-diaminobenzene, benzidine,
bis(2,2'-piperazino)-1,2-ethene, 1,4-diazabicyclo[2.2.2]octane,
naphthylethylenediamine, and 1,2-dianilinoethane. N Valence
Stabilizer #3: Examples of triamines (N--N bidentates or N--N
tridentates) that meet the requirements for use as "wide band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
N-(2-aminoethyl)-1,2-ethanediamine (dien, 2,2-tri);
N-(2-aminoethyl)-1,3-propanediamine (2,3-tri);
N-(3aminopropyl)-1,3-propanediamine (3,3-tri, dpt);
N-(3-aminopropyl)-1,4-butanediamine (3,4-tri, spermidine);
N-(2-aminoethyl)-1,4-butanediamine (2,4-tri);
N-(6-hexyl)-1,6-hexanediamine (6,6-tri); 1,3,5-triaminocyclohexane
(tach); 2-(aminomethyl)-1,3-propanediamine (tamm);
2-(aminomethyl)-2-methyl-1,3-propanediamine (tame);
2-(aminomethyl)-2-ethyl-1,3-propanediamine (lamp);
1,2,3-triaminopropane (tap); 2,3-(2-aminoethyl)aziridine;
2,4-(aminomethyl)azetidine; 2,5-(aminomethyl)pyrrolidine;
2,6-(aminomethyl)piperidine; di(2-aminobenzyl)amine;
hexahydro-1,3,5-triazine; hexahydro-2,4,6-trimethyl-1,3,5-triazine;
and 1,3,5-tris(aminomethyl)benzene. N Valence Stabilizer #4:
Examples of tetramines (N--N bidentates, N--N tridentates, or N--N
tetradentates) that meet the requirements for use as "wide band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
N,N'-(2-aminoethyl)-1,2-ethanediamine (2,2,2-tet, trien
(triethylenetetramine)); N,N'-(2-aminoethyl)-1,3-propanediamine
(2,3,2-tet, entnen); N,N'-(3-aminopropyl)-1,2-ethanediamine
(3,2,3-tet, tnentn);
N-(2-aminoethyl)-N'-(3-aminopropyl)-1,2-ethanediamine (2,2,3-tet);
N-(2-aminoethyl)-N'-(3-aminopropyl)-1,3-propanediamine (3,3,2-tet);
N,N'-(3-aminopropyl)-1,3-propanediamine (3,3,3-tet);
N,N'-(3-aminopropyl)-1,4-butanediamine (3,4,3-tet, spermine);
tri(aminomethyl)amine (tren); tri(2-aminoethyl)amine (trtn);
tri(3-aminopropyl)amine (trbn); 2,2-aminomethyl-1,3-propanediamine
(tam); 1,2,3,4-tetraminobutane (tab);
N,N'-(2-aminophenyl)-1,2-ethanediamine; and
N,N'-(2-aminophenyl)-1,3-propanediamine. N Valence Stabilizer #5:
Examples of pentamines (N--N bidentates, N--N tridentates, or N--N
tetradentates) that meet the requirements for use as "wide band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
N-[N-(2-aminoethyl)-2-aminoethyl]-N'-(2-aminoethyl)-1,2-ethanediamine
(2,2,2,2-pent, tetren);
N-[N-(3-aminopropyl)-2-aminoethyl]-N'-(3-aminopropyl)-1,2-ethanediamine
(3,2,2,3-pent);
N-[N-(3-aminopropyl)-3-aminopropyl]-N'-(3-aminopropyl)-1,3-propanediamine
(3,3,3,3-pent, caldopentamine);
N-[N-(2-aminobenzyl)-2-aminoethyl]-N'-(2-aminopropyl)-1,2-ethanediamine;
N-[N-(2-aminoethyl)-2-aminoethyl]-N,N-(2-aminoethyl)amine (trenen);
and N-[N-(2-aminopropyl)-2-aminoethyl]-N,N-(2-aminoethyl)amine
(4-Me-trenen). N Valence Stabilizer #6: Examples of hexamines (N--N
bidentates, N--N tridentates, N--N tetradentates, or
N--N--N--N--N--N hexadentates) that meet the requirements for use
as "wide band" valence stabilizers for Co.sup.+3 include, but are
not limited to:
N,N'-[N-(2-aminoethyl)-2-aminoethyl]-1,2-ethanediamine
(2,2,2,2,2-hex, linpen);
N,N'-[N-(2-aminoethyl)-3-aminopropyl]-1,2-ethanediamine
(2,3,2,3,2-hex); N,N,N',N'-(2-aminoethyl)-1,2-ethanediamine
(penten, ten); N,N,N',N '-(2-aminoethyl)-1-methyl-1,2-ethanediamine
(tpn, R-5-Me-penten); N,N,N',N'-(2-aminoethyl)-1,3-propanediamine
(ttn); N,N,N',N'-(2-aminoethyl)-1,4-butanediamine (tbn);
N,N,N',N'-(2-aminoethyl)-1,3-dimethyl-1,3-propanediamine (R,R-tptn,
R,S-tptn);
N-(2-aminoethyl)-2,2-[N-(2-aminoethyl)aminomethyl-1-propaneamine
(sen); and
N-(3-aminopropyl)-2,2-[N-(3-aminopropyl)aminomethyl-1-propaneamine
(stn). N Valence Stabilizer #7a: Examples of 5-membered
heterocyclic rings containing one nitrogen atom (N monodentates)
that meet the requirements for use as "wide band" valence
stabilizers for Co.sup.+3 include, but are not limited to:
1-pyrroline, 2-pyrroline, 3-pyrroline, pyrrole, oxazole, isoxazole,
thiazole, isothiazole, azaphosphole, benzopyrroline, benzopyrrole
(indole), benzoxazole, benzisoxazole, benzothiazole,
benzisothiazole, benzazaphosphole, dibenzopyrroline, dibenzopyrrole
(carbazole), dibenzoxazole, dibenzisoxazole, dibenzothiazole,
dibenzisothiazole, naphthopyrroline, naphthopyrrole, naphthoxazole,
naphthisoxazole, naphthothiazole, naphthisothiazole,
naphthazaphosphole, and polypyrroles. N Valence Stabilizer #7b:
Examples of 5-membered heterocyclic rings containing two nitrogen
atoms (N monodentates or N--N bidentates) that meet the
requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to: pyrazoline, imidazoline,
imidazole (ia), pyrazole, oxadiazole, thiadiazole, diazaphosphole,
benzopyrazoline, benzimidazoline, benzimidazole
(azindole)(bia)(bz), benzopyrazole (indazole), benzothiadiazole
(piazthiole), benzoxadiazole (benzofurazan), naphthopyrazoline,
naphthimidazoline, naphthimidazole, naphthopyrazole,
naphthoxadiazole, naphthothiadiazole, polybenzimidazole, and
polyimidazoles (e.g. polyvinylimidazole (pvi)). N Valence
Stabilizer #7c: Examples of 5-membered heterocyclic rings
containing three nitrogen atoms (N monodentates, N--N bidentates)
that meet the requirements for use as "wide band" valence
stabilizers for Co.sup.+3 include, but are not limited to:
triazole, oxatriazole, thiatriazole, benzotriazole (bta),
tolyltriazole (tt), naphthotriazole, and triazolophthalazine. N
Valence Stabilizer #7d: Examples of 5-membered heterocyclic rings
containing four nitrogen atoms (N monodentates or N--N bidentates)
that meet the requirements for use as "wide band" valence
stabilizers for Co.sup.+3 include, but are not limited to:
tetrazole. N Valence Stabilizer #8a: Examples of 6-membered
heterocyclic rings containing one nitrogen atom (N monodentates)
that meet the requirements for use as "wide band" valence
stabilizers for Co.sup.+3 include, but are not limited to:
pyridine, picoline, lutidine, .gamma.-collidine, oxazine, thiazine,
azaphosphorin, quinoline, isoquinoline, benzoxazine, benzothiazine,
benzazaphosphorin, acridine, phenanthridine, phenothiazine
(dibenzothiazine), dibenzoxazine, dibenzazaphosphorin,
benzoquinoline (naphthopyridine), naphthoxazine, naphthothiazine,
naphthazaphosphorin, and polypyridines. N Valence Stabilizer #8b:
Examples of 6-membered heterocyclic rings containing two nitrogen
atoms (N monodentates or N--N bidentates) that meet the
requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to: pyrazine, pyridazine,
pyrimidine, oxadiazine, thiadiazine, diazaphosphorin, quinoxaline
(benzopyrazine), cinnoline (benzo[c]pyridazine), quinazoline
(benzopyrimidine), phthalazine (benzo[d]pyridazine),
benzoxadiazine, benzothiadiazine, phenazine (dibenzopyrazine),
dibenzopyridazine, naphthopyrazine, naphthopyridazine,
naphthopyrimidine, naphthoxadiazine, naphthothiadiazine, and
polyquinoxalines. N Valence Stabilizer #8c: Examples of 6-membered
heterocyclic rings containing three nitrogen atoms (N monodentates
or N--N bidentates) that meet the requirements for use as "wide
band" valence stabilizers for Co.sup.+3 include, but are not
limited to: 1,3,5-triazine, 1,2,3-triazine, benzo-1,2,3-triazine,
naphtho-1,2,3-triazine, oxatriazine, thiatriazine, melamine, and
cyanuric acid. N Valence Stabilizer #8d: Examples of 6-membered
heterocyclic rings containing four nitrogen atoms (N monodentates
or N--N bidentates) that meet the requirements for use as "wide
band" valence stabilizers for Co.sup.+3 include, but are not
limited to: tetrazine. N Valence Stabilizer #9a: Examples of
5-membered heterocyclic rings containing one nitrogen atom and
having at least one additional nitrogen atom binding site not
contained in a ring (N Monodentates, N--N Bidentates, N--N
Tridentates, N--N Tetradentates, or N--N Hexadentates) that meet
the requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to:
2-(aminomethyl)-3-pyrroline; 2,5-(aminomethyl)-3-pyrroline;
2-(aminomethyl)pyrrole; 2,5-(aminomethyl)pyrrole;
3-(aminomethyl)isoxazole; 2-(aminomethyl)thiazole;
3-(aminomethyl)isothiazole; 2-(aminomethyl)indole;
2-aminobenzoxazole; 2-aminobenzothiazole (abt);
1,8-diaminocarbazole; 2-amino-6-methyl-benzothiazole (amebt);
2-amino-6-methoxybenzothiazole (ameobt); and
1,3-diiminoisoindoline. N Valence Stabilizer #9b: Examples of
5-membered heterocyclic rings containing two nitrogen atoms at
least one additional nitrogen atom binding site not contained in a
ring (N Monodentates, N--N Bidentates, N--N Tridentates, N--N
Tetradentates, or N--N Hexadentates) that meet the requirements for
use as "wide band" valence stabilizers for Co.sup.+3 include, but
are not limited to: 2-aminoimidazoline;
1-(3-aminopropyl)imidazoline; 2-aminoimidazole;
1-(3-aminopropyl)imidazole; 4-(2-aminoethyl)imidazole [histamine];
1-alkyl-4-(2-aminoethyl)imidazole; 3-(2-aminoethyl)pyrazole;
3,5-(2-aminoethyl)pyrazole; I-(aminomethyl)pyrazole;
2-aminobenzimidazole; 7-(2-aminoethyl)benzimidazole;
1-(3-aminopropyl)benzimidazole; 3-(2-aminoethyl)indazole;
3,7-(2-aminoethyl)indazole; I-(aminomethyl)indazole;
7-aminobenzothiadiazole; 4-(2-aminoethyl)benzothiadiazole;
7-aminobenzoxadiazole; 4-(2-aminoethyl)benzoxadiazole;
ethylenediaminetetra(1-pyrazolylmethane) [edtp];
methylenenitrilotris(2-(1-methyl)benzimidazole) [mntb]
[tris(1-methyl-2-benzimidazolylmethane)amine];
bis(alkyl-1-pyrazolylmethane)amine;
bis(alkyl-2-(1-pyrazolyl)ethane)amine;
bis(N,N-(2-benzimidazolyl)-2-aminoethane)(2-benzimidazolylmethane)amine;
bis(1-(3,5-dimethyl)pyrazolylmethane)phenylamine;
tris(2-(1-(3,5-dimethyl)pyrazolyl)ethane)amine;
5-(dimethylamino)pyrazole; 5-(dimethylaminomethyl)pyrazole;
2-amino-1,3,4-thiadiazole; and 1-(2-aminoethyl)imidazoline. N
Valence Stabilizer #9c: Examples of 5-membered heterocyclic rings
containing three nitrogen atoms at least one additional nitrogen
atom binding site not contained in a ring (N Monodentates, N--N
Bidentates, N--N--N Tridentates, N--N--N--N Tetradentates, or
N--N--N--N--N--N Hexadentates) that meet the requirements for use
as "wide band" valence stabilizers for Co.sup.+3 include, but are
not limited to: 3-amino-1,2,4-triazole (ata);
3,5-diamino-1,2,4-triazole (dat); 5-amino-1,2,4-triazole;
3-(2-aminoethyl)-1,2,4-triazole; 5-(2-aminoethyl)-1,2,4-triazole;
3,5-(2-aminoethyl)-1,2,4-triazole; 1-(aminomethyl)-1,2,4-triazole;
3,5-(aminomethyl)-4-amino-1,2,4-triazole;
4-(2-aminoethyl)-1,2,3-triazole; 5-(2-aminoethyl)-1,2,3-triazole;
7-aminobenzotriazole; 1-(aminomethyl)-1,2,3-triazole;
1-(2-aminoethyl)-1,2,3-triazole; 4-(3-aminopropyl)benzotriazole;
N-(benzotriazolylalkyl)amine; dibenzotriazole-1-ylalkylamine;
bis(5-amino-1,2,4-triazol-3-yl);
bis(5-amino-1,2,4-triazol-3-yl)alkanes; and
1-(aminomethyl)benzotriazole. N Valence Stabilizer #9d: Examples of
5-membered heterocyclic rings containing four nitrogen atoms at
least one additional nitrogen atom binding site not contained in a
ring (N Monodentates, N--N Bidentates, N--N Tridentates, N--N
Tetradentates, or N--N Hexadentates) that meet the requirements for
use as "wide band" valence stabilizers for Co.sup.+3 include, but
are not limited to: 5-(2-aminoethyl)-1H-tetrazole;
1-(aminomethyl)-1H-tetrazole; and 1-(2-aminoethyl)-1H-tetrazole. N
Valence Stabilizer #10a: Examples of 6-membered heterocyclic rings
containing one nitrogen atom and having at least one additional
nitrogen atom binding site not contained in a ring (N Monodentates,
N--N Bidentates, N--N Tridentates, N--N Tetradentates, or N--N
Hexadentates) that meet the requirements for use as "wide band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
2-aminopyridine; 2,6-diaminopyridine; 2-(aminomethyl)pyridine;
2,6-(aminomethyl)pyridine; 2,6-(aminoethyl)pyridine;
2-amino-4-picoline; 2,6-diamino-4-picoline; 2-amino-3,5-lutidine;
2-aminoquinoline; 8-aminoquinoline; 2-aminoisoquinoline;
acriflavine; 4-aminophenanthridine; 4,5-(aminomethyl)phenothiazine;
4,5-(aminomethyl)dibenzoxazine; 10-amino-7,8-benzoquinoline;
bis(2-pyridylmethane)amine; tris(2-pyridyl)amine;
bis(4-(2-pyridyl)-3-azabutane)amine;
bis(N,N-(2-(2-pyridyl)ethane)aminomethane)amine;
4-(N,N-dialkylaminomethyl)morpholine; 6-aminonicotinic acid;
8-aminoacridine; and 2-hydrazinopyridine. N Valence Stabilizer
#10b: Examples of 6-membered heterocyclic rings containing two
nitrogen atoms at least one additional nitrogen atom binding site
not contained in a ring (N Monodentates, N--N Bidentates, N--N
Tridentates, N--N Tetradentates, or N--N Hexadentates) that meet
the requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to: 2-aminopyrazine;
2,6-diaminopyrazine; 2-(aminomethyl)pyrazine;
2,6-(aminomethyl)pyrazine; 3-(aminomethyl)pyridazine;
3,6-(aminomethyl)pyridazine; 3,6-(2-aminoethyl)pyridazine;
1-aminopyridazine; 1-(aminomethyl)pyridazine; 2-aminopyrimidine;
1-(2-aminoethyl)pyrimidine; 2-aminoquinoxaline;
2,3-diaminoquinoxaline; 2-aminocinnoline; 3-aminocinnoline;
3-(2-aminoethyl)cinnoline; 3,8-(2-aminoethyl)cinnoline;
2-aminoquinazoline; 1-(2-aminoethyl)quinazoline;
1-aminophthalazine; 1,4-(2-aminoethyl)phthalazine;
1,8-(aminomethyl)phenazine; 2-amino-4,6-dimethylpyrimidine (admp);
dihydralazine; and hydralazine. N Valence Stabilizer #10c: Examples
of 6-membered heterocyclic rings containing three nitrogen atoms at
least one additional nitrogen atom binding site not contained in a
ring (N Monodentates, N--N Bidentates, N--N Tridentates, N--N
Tetradentates, or N--N Hexadentates) that meet the requirements for
use as "wide band" valence stabilizers for Co.sup.+3 include, but
are not limited to: 2-amino-1,3,5-triazine;
2-(aminomethyl)-1,3,5-triazine; 2,6-(aminomethyl)-1,3,5-triazine;
1-(3-aminopropyl)-1,3,5-triazine;
1,5-(3-aminopropyl)-1,3,5-triazine; polymelamines; melamine; and
altretamine. N Valence Stabilizer #10d: Examples of 6-membered
heterocyclic rings containing four nitrogen atoms at least one
additional nitrogen atom binding site not contained in a ring (N
Monodentates, N--N Bidentates, N--N Tridentates, N--N
Tetradentates, or N--N Hexadentates) that meet the requirements for
use as "wide band" valence stabilizers for Co.sup.+3 include, but
are not limited to: 3,6-(2-aminoethyl)-1,2,4,5-tetrazine;
3,6-(1,3-diamino-2-propyl)-1,2,4,5-tetrazine; and
4,6-(aminomethyl)-1,2,3,5-tetrazine. N Valence Stabilizer #11a:
Examples of 5-membered heterocyclic rings containing one nitrogen
atom and having at least one additional nitrogen atom binding site
contained in a ring (N
Monodentates, N--N Bidentates, N--N Tridentates, N--N
Tetradentates) that meet the requirements for use as "wide band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
2,2'-bi-3-pyrroline; 2,2'-bi-2-pyrroline; 2,2'-bi-1-pyrroline;
2,2'-bipyrrole; 2,2',2''-tripyrrole; 3,3'-biisoxazole;
2,2'-bioxazole; 3,3'-biisothiazole; 2,2'-bithiazole; 2,2'-biindole;
2,2'-bibenzoxazole; 2,2'-bibenzothiazole; bilirubin; biliverdine;
and 7-azaindole. N Valence Stabilizer #11b: Examples of 5-membered
heterocyclic rings containing two nitrogen atoms at least one
additional nitrogen atom binding site contained in a ring (N
Monodentates, N--N Bidentates, N--N Tridentates, N--N
Tetradentates) that meet the requirements for use as "wide band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
2,2'-bi-2-imidazoline [2,2'-bi-2-imidazolinyl][bimd];
2,2'-biimidazole [2,2'-biimidazolyl][biimH.sub.2]; 5,5'-bipyrazole;
3,3'-bipyrazole; 4,4'-bipyrazole [4,4'-bipyrazolyl][bpz];
2,2'-bioxadiazole; 2,2'-bithiadiazole; 2,2'-bibenzimidazole;
7,7'-biindazole; 5,5'-bibenzofurazan; 5,5'-bibenzothiadiazole;
bis-1,2-(2-benzimidazole)ethane; bis(2-benzimidazole)methane;
1,2-(2-imidazolyl)benzene; 2-(2-thiazolyl)benzimidazole;
2-(2-imidazolyl)benzimidazole; benzimidazotriazine;
4-azabenzimidazole; and 2,6-bis(2-benzimidazolyl)pyridine. N
Valence Stabilizer #11c: Examples of 5-membered heterocyclic rings
containing three nitrogen atoms at least one additional nitrogen
atom binding site contained in a ring (N Monodentates, N--N
Bidentates, N--N Tridentates, N--N Tetradentates) that meet the
requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to: 5,5'-bi-1,2,4-triazole
[btrz]; 3,3'-bi-1,2,4-triazole; 1,1'-bi-1,2,4-triazole;
1,1'-bi-1,2,3-triazole; 5,5'-bi-1,2,3-triazole;
7,7'-bibenzotriazole; 1,1'-bibenzotriazole;
bis(pyridyl)aminotriazole (pat); and 8-azaadenine. N Valence
Stabilizer #11d: Examples of 5-membered heterocyclic rings
containing four nitrogen atoms at least one additional nitrogen
atom binding site contained in a ring (N Monodentates, N--N
Bidentates, N--N Tridentates, N--N Tetradentates) that meet the
requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to: 5,5'-bi-1H-tetrazole;
and 1,1'-bi-1H-tetrazole. N Valence Stabilizer #12a: Examples of
6-membered heterocyclic rings containing one nitrogen atom and
having at least one additional nitrogen atom binding site contained
in a ring (N Monodentates, N--N Bidentates, N--N Tridentates, N--N
Tetradentates) that meet the requirements for use as "wide band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
2,2'-bipyridine [bipy]; 2,2',2''-tripyridine [terpyridine] [terpy];
2,2',2'',2'''-tetrapyridine [tetrapy]; 6,6'-bi-2-picoline;
6,6'-bi-3-picoline; 6,6'-bi-4-picoline; 6,6'-bi-2,3-lutidine;
6,6'-bi-2,4-lutidine; 6,6'-bi-3,4-lutidine;
6,6'-bi-2,3,4-collidine; 2,2'-biquinoline; 2,2'-biisoquinoline;
3,3'-bibenzoxazine; 3,3'-bibenzothiazine; 1,10-phenanthroline
[phen]; 1,8-naphthyridine; bis-1,2-(6-(2,2'-bipyridyl))ethane;
bis-1,3-(6-(2,2'-bipyridyl))propane; 3,5-bis(3-pyridyl)pyrazole;
3,5-bis(2-pyridyl)triazole; 1,3-bis(2-pyridyl)-1,3,5-triazine;
1,3-bis(2-pyridyl)-5-(3-pyridyl)-1,3,5-triazine;
2,7-(N,N'-di-2-pyridyl)diaminobenzopyrroline;
2,7-(N,N'-di-2-pyridyl)diaminophthalazine;
2,6-di-(2-benzothiazolyl)pyridine; triazolopyrimidine;
2-(2-pyridyl)imidazoline; 7-azaindole; 1-(2-pyridyl)pyrazole;
(1-imidazolyl)(2-pyridyl)methane;
4,5-bis(N,N'-(2-(2-pyridyl)ethyl)iminomethyl)imidazole;
bathophenanthroline; 4-(2-benzimidazolyl)quinoline;
1,2-bis(2-pyridyl)ethane; 4,4'-diphenyl-2,2'-dipyridyl;
neocuproine; nicotine; and nornicotine. N Valence Stabilizer #12b:
Examples of 6-membered heterocyclic rings containing two nitrogen
atoms at least one additional nitrogen atom binding site contained
in a ring (N Monodentates, N--N Bidentates, N--N Tridentates, N--N
Tetradentates) that meet the requirements for use as "wide band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
2,2'-bipyrazine; 2,2',2''-tripyrazine; 6,6'-bipyridazine;
bis(3-pyridazinyl)methane-1,2-bis(3-pyridazinyl)ethane;
2,2'-bipyrimidine; 2,2'-biquinoxaline; 8,8'-biquinoxaline;
bis(3-cinnolinyl)methane; bis(3-cinnolinyl)etbane;
8,8'-bicinnoline; 2,2'-biquinazoline; 4,4'-biquinazoline;
8,8'-biquinazoline; 2,2'-biphthalazine; 1,1'-biphthalazine;
2-(2-pyridyl)benzimidazole; 8-azapurine; purine; adenine; guanine;
hypoxanthine;
2,6-bis(N,N'-(2-(4-imidazolyl)ethyl)iminomethyl)pyridine;
2-(N-(2-(4-imidazolyl)ethyl)iminomethyl)pyridine; adenine
(aminopurine); purine; and 2,3-bis(2-pyridyl)pyrazine. N Valence
Stabilizer #12c: Examples of 6-membered heterocyclic rings
containing three nitrogen atoms at least one additional nitrogen
atom binding site contained in a ring (N Monodentates, N--N
Bidentates, N--N Tridentates, N--N Tetradentates) that meet the
requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to: 2,2'-bi-1,3,5-triazine;
2,2',2''-tri-1,3,5-triazine; 4,4'-bi-1,2,3-triazine; and
4,4'-bibenzo-1,2,3-triazine; 2,4,6-tris(2-pyridyl)-1,3,5-triazine;
and benzimidazotriazines. N Valence Stabilizer #12d: Examples of
6-membered heterocyclic rings containing four nitrogen atoms at
least one additional nitrogen atom binding site contained in a ring
(N Monodentates, N--N Bidentates, N--N Tridentates, N--N
Tetradentates) that meet the requirements for use as "wide band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
3,3'-bi-1,2,4,5-tetrazine; and 4,4'-bi-1,2,3,5-tetrazine. N Valence
Stabilizer #13a: Examples of two-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein both binding sites
are composed of nitrogen (usually amine or imine groups) and are
not contained in component heterocyclic rings (N--N Bidentates)
that meet the requirements for use as "wide band" valence
stabilizers for Co.sup.+3 include, but are not limited to:
diazacyclobutane ([4]aneN.sub.2); diazacyclopentane
([5]aneN.sub.2); diazacyclohexane ([6]aneN.sub.2);
diazacycloheptane ([7]aneN.sub.2); diazacyclooctane
([8]aneN.sub.2); piperazine; benzopiperazine; diazacyclobutene
([4]eneN.sub.2); diazacyclopentene ([5]eneN.sub.2);
diazacyclohexene ([6]eneN.sub.2); diazacycloheptene
([7]eneN.sub.2); diazacyclooctene ([8]eneN.sub.2);
diazacyclobutadiene ([4]dieneN.sub.2); diazacyclopentadiene
([5]dieneN.sub.2); diazacyclohexadiene ([6]dieneN.sub.2);
diazacycloheptadiene ([7]dieneN.sub.2); and diazacyclooctadiene
([8]dieneN.sub.2). N Valence Stabilizer #13b: Examples of
three-membered macrocyclics, macrobicyclics, and macropolycyclics
(including catapinands, cryptands, cyclidenes, and sepulchrates)
wherein all binding sites are composed of nitrogen (usually amine
or imine groups) and are not contained in component heterocyclic
rings (N--N Tridentates) that meet the requirements for use as
"wide band" valence stabilizers for Co.sup.+3 include, but are not
limited to: triazacyclohexane (including
hexahydro-1,3,5-triazine)([6]aneN.sub.3); triazacycloheptane
([7]aneN.sub.3); triazacyclooctane ([8]aneN.sub.3);
triazacyclononane ([9]aneN.sub.3); triazacyclodecane
([10]aneN.sub.3); triazacycloundecane ([11]aneN.sub.3);
triazacyclododecane ([12]aneN.sub.3); triazacyclohexene
([6]eneN.sub.3); triazacycloheptene ([7]eneN.sub.3);
triazacyclooctene ([8]eneN.sub.3); triazacyclononene
([9]eneN.sub.3); triazacyclodecene ([10]eneN.sub.3);
triazacycloundecene ([11]eneN.sub.3); triazacyclododecene
([12]eneN.sub.3); triazacyclohexatriene ([6]trieneN.sub.3);
triazacycloheptatriene ([7]trieneN.sub.3); triazacyclooctatriene
([8]trieneN.sub.3); triazacyclononatriene ([9]trieneN.sub.3);
triazacyclodecatriene ([10]trieneN.sub.3); triazacycloundecatriene
([11]trieneN.sub.3); and triazacyclododecatriene
([12]trieneN.sub.3). N Valence Stabilizer #13c: Examples of
four-membered macrocyclics, macrobicyclics, and macropolycyclics
(including catapinands, cryptands, cyclidenes, and sepulchrates)
wherein all binding sites are composed of nitrogen (usually amine
or imine groups) and are not contained in component heterocyclic
rings (N--N Tetradentates) that meet the requirements for use as
"wide band" valence stabilizers for Co.sup.+3 include, but are not
limited to: tetraazacyclooctane ([8]aneN.sub.4);
tetraazacyclononane ([9]aneN.sub.4); tetraazacyclodecane
([10]aneN.sub.4); tetraazacycloundecane ([11]aneN.sub.4);
tetraazacyclododecane ([12]aneN.sub.4); tetraazacyclotridecane
([13]aneN.sub.4); tetraazacyclotetradecane ([14]aneN.sub.4);
tetraazacyclopentadecane ([15]aneN.sub.4); tetraazacyclohexadecane
([16]aneN.sub.4); tetraazacycloheptadecane ([17]aneN.sub.4);
tetraazacyclooctadecane ([18]aneN.sub.4); tetraazacyclononadecane
([19]aneN.sub.4); tetraazacycloeicosane ([20]aneN.sub.4);
tetraazacyclooctadiene ([8]dieneN.sub.4); tetraazacyclononadiene
([9]dieneN.sub.4); tetraazacyclodecadiene ([10]dieneN.sub.4);
tetraazacycloundecadiene ([11]dieneN.sub.4);
tetraazacyclododecadiene ([12]dieneN.sub.4);
tetraazacyclotridecadiene ([13]dieneN.sub.4);
tetraazacyclotetradecadiene ([14]dieneN.sub.4);
tetraazacyclopentadecadiene ([15]dieneN.sub.4);
tetraazacyclohexadecadiene ([16]dieneN.sub.4);
tetraazacycloheptadecadiene ([17]dieneN.sub.4);
tetraazacyclooctadecadiene ([18]dieneN.sub.4);
tetraazacyclononadecadiene ([19]dieneN.sub.4);
tetraazacycloeicosadiene ([20]dieneN.sub.4);
tetraazacyclooctatetradiene ([8]tetradieneN.sub.4);
tetraazacyclononatetradiene ([9]tetradieneN.sub.4);
tetraazacyclodecatetradiene ([10]tetradieneN.sub.4);
tetraazacycloundecatetradiene ([11]tetradieneN.sub.4);
tetraazacyclododecatetradiene ([12]tetradieneN.sub.4);
tetraazacyclotridecatetradiene ([13]tetradieneN.sub.4);
tetraazacyclotetradecatetradiene ([14]tetradieneN.sub.4);
tetraazacyclopentadecatetradiene ([15]tetradieneN.sub.4);
tetraazacyclohexadecatetradiene ([16]tetradieneN.sub.4);
tetraazacycloheptadecatetradiene ([17]tetradieneN.sub.4);
tetraazacyclooctadecatetradiene ([18]tetradieneN.sub.4);
tetraazacyclononadecatetradiene ([19]tetradieneN.sub.4); and
tetraazacycloeicosatetradiene ([20]tetradieneN.sub.4). N Valence
Stabilizer #13d: Examples of six-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all binding sites
are composed of nitrogen (usually amine or imine groups) and are
not contained in component heterocyclic rings (N--N Tridentates,
N--N Tetradentates, or N--N Hexadentates) that meet the
requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to: hexaazacyclododecane
([12]aneN.sub.6); hexaazacyclotridecane ([13]aneN.sub.6);
hexaazacyclotetradecane ([14]aneN.sub.6); hexaazacyclopentadecane
([15]aneN.sub.6); hexaazacyclohexadecane ([16]aneN.sub.6);
hexaazacycloheptadecane ([17]aneN.sub.6); hexaazacyclooctadecane
([18]aneN.sub.6); hexaazacyclononadecane ([19]aneN.sub.6);
hexaazacycloeicosane ([20]aneN.sub.6); hexaazacycloheneicosane
([21]aneN.sub.6); hexaazacyclodocosane ([22]aneN.sub.6);
hexaazacyclotricosane ([23]aneN.sub.6); hexaazacyclotetracosane
([24]aneN.sub.6); hexaazacyclododecatriene ([12]trieneN.sub.6);
hexaazacyclotridecatriene ([13]trieneN.sub.6);
hexaazacyclotetradecatriene ([14]trieneN.sub.6);
hexaazacyclopentadecatriene ([15]trieneN.sub.6);
hexaazacyclohexadecatriene ([16]trieneN.sub.6);
hexaazacycloheptadecatriene ([17]trieneN.sub.6);
hexaazacyclooctadecatriene ([18]trieneN.sub.6);
hexaazacyclononadecatriene ([19]trieneN.sub.6);
hexaazacycloeicosatriene ([20]trieneN.sub.6);
hexaazacycloheneicosatriene ([21]trieneN.sub.6);
hexaazacyclodocosatriene ([22]trieneN.sub.6);
hexaazacyclotricosatriene ([23]trieneN.sub.6); and
hexaazacyclotetracosatriene ([24]trieneN.sub.6). N Valence
Stabilizer #13e: Examples of eight-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all binding sites
are composed of nitrogen (usually amine or imine groups) and are
not contained in component heterocyclic rings (N--N Tridentates,
N--N Tetradentates, or N--N Hexadentates) that meet the
requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to: octaazacyclohexadecane
([16]aneN.sub.8); octaazacycloheptadecane ([17]aneN.sub.8);
octaazacyclooctadecane ([18]aneN.sub.8); octaazacyclononadecane
([19]aneN.sub.8); octaazacycloeicosane ([20]aneN.sub.8);
octaazacycloheneicosane ([21]aneN.sub.8); octaazacyclodocosane
([22]aneN.sub.8); octaazacyclotricosane ([23]aneN.sub.8);
octaazacyclotetracosane ([24]aneN.sub.8);
octaazacyclohexadecatetradiene ([16] tetradieneN.sub.8);
octaazacycloheptadecatetradiene ([17]tetradieneN.sub.8);
octaazacyclooctadecatetradiene ([18]tetradieneN.sub.8);
octaazacyclononadecatetradiene ([19]tetradieneN.sub.8);
octaazacycloeicosatetradiene ([20]tetradieneN.sub.8);
octaazacycloheneicosatetradiene ([21]tetradieneN.sub.8);
octaazacyclodocosatetradiene ([22]tetradieneN.sub.8);
octaazacyclotricosatetradiene ([23]tetradieneN.sub.8); and
octaazacyclotetracosatetradiene ([24]tetradieneN.sub.8). N Valence
Stabilizer #13f: Examples of ten-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all binding sites
are composed of nitrogen (usually amine or imine groups) and are
not contained in component heterocyclic rings (N--N Tridentates,
N--N Tetradentates, or N--N Hexadentates) that meet the
requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to: decaazacycloeicosane
([20]aneN.sub.10); decaazacycloheneicosane ([21]aneN.sub.10);
decaazacyclodocosane ([22]aneN.sub.10); decaazacyclotricosane
([23]aneN.sub.10); decaazacyclotetracosane ([24]aneN.sub.10);
decaazacyclopentacosane ([25]aneN.sub.10); decaazacyclohexacosane
([26]aneN.sub.10); decaazacycloheptacosane ([27]aneN.sub.10);
decaazacyclooctacosane ([28]aneN.sub.10); decaazacyclononacosane
([29]aneN.sub.10); decaazacyclotriacontane ([30]aneN.sub.10);
decaazacycloeicosapentadiene ([20]pentadieneN.sub.10);
decaazacycloheneicosapentadiene ([21]pentadieneN.sub.10);
decaazacyclodocosapentadiene ([22]pentadieneN.sub.10);
decaazacyclotricosapentadiene ([23]pentadieneN.sub.10);
decaazacyclotetracosapentadiene ([24]pentadieneN.sub.10);
decaazacyclopentacosapentadiene ([25]pentadieneN.sub.10);
decaazacyclohexacosapentadiene ([26]pentadieneN.sub.10);
decaazacycloheptacosapentadiene ([27]pentadieneN.sub.10);
decaazacyclooctacosapentadiene ([28]pentadieneN.sub.10);
decaazacyclononacosapentadiene ([29]pentadieneN.sub.10); and
decaazacyclotriacontapentadiene ([30]pentadieneN.sub.10). N Valence
Stabilizer #14a: Examples of four-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all four binding
sites are composed of nitrogen and are contained in component
5-membered heterocyclic rings (N--N Tetradentates) that meet the
requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to: porphyrins (including
tetraphenylporphine (tpp); "picket fence" porphyrins, "picket tail"
porphyrins, "bispocket" porphyrins, "capped" porphyrins, cyclophane
porphyrins, "pagoda" porphyrins, "pocket" porphyrins, "pocket tail"
porphyrins, cofacial diporphyrins, "strapped" porphyrins, "hanging
base" porphyrins, bridged porphyrins, chelated mesoporphyrins,
homoporphyrins, chlorophylls, and pheophytins); porphodimethanes;
porphyrinogens; chlorins; bacteriochlorins; isobacteriochlorins;
corroles; corrins and corrinoids; didehydrocorrins;
tetradehydrocorrins; hexadehydrocorrins; octadehydrocorrins;
tetraoxazoles; tetraisooxazoles; tetrathiazoles; tetraisothiazoles;
tetraazaphospholes; tetraimidazoles; tetrapyrazoles;
tetraoxadiazoles; tetrathiadiazoles; tetradiazaphospholes;
tetratriazoles; tetraoxatriazoles; tetrathiatriazoles;
coproporphyrin; etioporphyrin; and hematoporphyrin. N Valence
Stabilizer #14b: Examples
of six-membered macrocyclics, macrobicyclics, and macropolycyclics
(including catapinands, cryptands, cyclidenes, and sepulchrates)
wherein all six binding sites are composed of nitrogen and are
contained in component 5-membered heterocyclic rings (N--N
Tridentates, N--N Tetradentates, or N--N Hexadentates) that meet
the requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to: hexaphyrins
(hexapyrroles); hexaoxazoles; hexaisooxazoles; hexathiazoles;
hexaisothiazoles; hexaazaphospholes; hexaimidazoles; hexapyrazoles;
hexaoxadiazoles; hexathiadiazoles; hexadiazaphospholes;
hexatriazoles; hexaoxatriazoles; and hexathiatriazoles. N Valence
Stabilizer #14c: Examples of eight-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all eight binding
sites are composed of nitrogen and are contained in component
5-membered heterocyclic rings (N--N Tridentates, N--N
Tetradentates, or N--N Hexadentates) that meet the requirements for
use as "wide band" valence stabilizers for Co.sup.+3 include, but
are not limited to: octaphyrins (octapyrroles); octaoxazoles;
octaisooxazoles; octathiazoles; octaisothiazoles;
octaazaphospholes; octaimidazoles; octapyrazoles; octaoxadiazoles;
octathiadiazoles; octadiazaphospholes; octatriazoles;
octaoxatriazoles; and octathiatriazoles. N Valence Stabilizer #14d:
Examples of ten-membered macrocyclics, macrobicyclics, and
macropolycyclics (including catapinands, cryptands, cyclidenes, and
sepulchrates) wherein all ten binding sites are composed of
nitrogen and are contained in component 5-membered heterocyclic
rings (N--N Tridentates, N--N Tetradentates, or N--N Hexadentates)
that meet the requirements for use as "wide band" valence
stabilizers for Co.sup.+3 include, but are not limited to:
decaphyrins (decapyrroles); decaoxazoles; decaisooxazoles;
decathiazoles; decaisothiazoles; decaazaphospholes; decaimidazoles;
decapyrazoles; decaoxadiazoles; decathiadiazoles;
decadiazaphospholes; decatriazoles; decaoxatriazoles; and
decathiatriazoles. N Valence Stabilizer #15a: Examples of
four-membered macrocyclics, macrobicyclics, and macropolycyclics
(including catapinands, cryptands, cyclidenes, and sepulchrates)
wherein all four binding sites are composed of nitrogen and are
contained in a combination of 5-membered heterocyclic rings and
amine or imine groups (N--N Tetradentates) that meet the
requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to: porphyrazines;
octahydrodiazaporphyrins; phthalocyanines; naphthalocyanines;
anthracocyanines; and tetraazaporphyrins N Valence Stabilizer #15b:
Examples of six-membered macrocyclics, macrobicyclics, and
macropolycyclics (including catapinands, cryptands, cyclidenes, and
sepulchrates) wherein all six binding sites are composed of
nitrogen and are contained in a combination of 5-membered
heterocyclic rings and amine or imine groups (N--N Tridentates,
N--N Tetradentates, or N--N Hexadentates) that meet the
requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to: diazahexaphyrins;
tetraazahexaphyrins; hexaazahexaphyrins; diazahexapyrazoles;
tetraazahexapyrazoles; hexaazahexapyrazoles; diazahexaimidazoles;
tetraazahexaimidazoles; and hexaazahexaimidazoles. N Valence
Stabilizer #15c: Examples of eight-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all eight binding
sites are composed of nitrogen and are contained in a combination
of 5-membered heterocyclic rings and amine or imine groups (N--N
Tridentates, N--N Tetradentates, or N--N Hexadentates) that meet
the requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to: diazaoctaphyrins;
tetraazaoctaphyrins; hexaazaoctaphyrins; octaazaoctaphyrins;
diazaoctapyrazoles; tetraazaoctapyrazoles; hexaazaoctapyrazoles;
octaazaoctapyrazoles; diazaoctaimidazoles; tetraazaoctaimidazoles;
hexaazaoctaimidazoles; and octaazaoctaimidazoles. N Valence
Stabilizer #15d: Examples of ten-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all ten binding
sites are composed of nitrogen and are contained in a combination
of 5-membered heterocyclic rings and amine or imine groups (N--N
Tridentates, N--N Tetradentates, or N--N Hexadentates) that meet
the requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to: diazadecaphyrins;
tetraazadecaphyrins; hexaazadecaphyrins; octaazadecaphyrins;
decaazadecaphyrins; diazadecapyrazoles; tetraazadecapyrazoles;
hexaazadecapyrazoles; octaazadecapyrazoles; decaazadecapyrazoles;
diazadecaimidazoles; tetraazadecaimidazoles; hexaazadecaimidazoles;
octaazadecaimidazoles; and decaazadecaimidazoles. N Valence
Stabilizer #16a: Examples of four-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all four binding
sites are composed of nitrogen and are contained in component
6-membered heterocyclic rings (N--N Tetradentates) that meet the
requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to: cyclotetrapyridines;
cyclotetraoxazines; cyclotetrathiazines; cyclotetraphosphorins;
cyclotetraquinolines; cyclotetrapyrazines; cyclotetrapyridazines;
cyclotetrapyrimidines; cyclotetraoxadiazines;
cyclotetrathiadiazines; cyclotetradiazaphosphorins;
cyclotetraquinoxalines; cyclotetratriazines;
cyclotetrathiatriazines; and cyclotetraoxatriazines. N Valence
Stabilizer #16b: Examples of six-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all six binding
sites are composed of nitrogen and are contained in component
6-membered heterocyclic rings (N--N Tridentates, N--N
Tetradentates, or N--N Hexadentates) that meet the requirements for
use as "wide band" valence stabilizers for Co.sup.+3 include, but
are not limited to: cyclosexipyridines; cyclosexioxazines;
cyclosexithiazines; cyclosexiphosphorins; cyclosexiquinolines;
cyclosexipyrazines; cyclosexipyridazines; cyclosexipyrimidines;
cyclosexioxadiazines; cyclosexithiadiazines;
cyclosexidiazaphosphorins cyclosexiquinoxalines;
cyclosexitriazines; cyclosexithiatriazines; and
cyclosexioxatriazines. N Valence Stabilizer #16c: Examples of
eight-membered macrocyclics, macrobicyclics, and macropolycyclics
(including catapinands, cryptands, cyclidenes, and sepulchrates)
wherein all six binding sites are composed of nitrogen and are
contained in component 6-membered heterocyclic rings (N--N
Tridentates, N--N Tetradentates, or N--N Hexadentates) that meet
the requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to: cyclooctapyridines;
cyclooctaoxazines; cyclooctathiazines; cyclooctaphosphorins;
cyclooctaquinolines; cyclooctapyrazines; cyclooctapyridazines;
cyclooctapyrimidines; cyclooctaoxadiazines; cyclooctathiadiazines;
cyclooctadiazaphosphorins; cyclooctaquinoxalines;
cyclooctatriazines; cyclooctathiatriazines; and
cyclooctaoxatriazines. N Valence Stabilizer #16d: Examples of
ten-membered macrocyclics, macrobicyclics, and macropolycyclics
(including catapinands, cryptands, cyclidenes, and sepulchrates)
wherein all six binding sites are composed of nitrogen and are
contained in component 6-membered heterocyclic rings (N--N
Tridentates, N--N Tetradentates, or N--N Hexadentates) that meet
the requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to: cyclodecapyridines;
cyclodecaoxazines; cyclodecathiazines; cyclodecaphosphorins;
cyclodecaquinolines; cyclodecapyrazines; cyclodecapyridazines;
cyclodecapyrimidines; cyclodecaoxadiazines; cyclodecathiadiazines;
cyclodecadiazaphosphorins; cyclodecaquinoxalines;
cyclodecatriazines; cyclodecathiatriazines; and
cyclodecaoxatriazines. N Valence Stabilizer #17a: Examples of
four-membered macrocyclics, macrobicyclics, and macropolycyclics
(including catapinands, cryptands, cyclidenes, and sepulchrates)
wherein all four binding sites are composed of nitrogen and are
contained in a combination of 6-membered heterocyclic rings and
amine or imine groups (N--N Tetradentates) that meet the
requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to:
diazacyclotetrapyridines; tetraazacyclotetrapyridines;
diazacyclotetraquinolines; tetraazacyclotetraquinolines;
diazacyclotetrapyrazines; tetraazacyclotetrapyrazines;
diazacyclotetrapyridazines; tetraazacyclotetrapyridazines;
diazacyclotetrapyrimidines; tetraazacyclotetrapyrimidines;
diazacyclotetratriazines; and tetraazacyclotetratriazines. N
Valence Stabilizer #17b: Examples of six-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all six binding
sites are composed of nitrogen and are contained in a combination
of 6-membered heterocyclic rings and amine or imine groups (N--N
Tridentates, N--N Tetradentates, or N--N Hexadentates) that meet
the requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to: diazacyclosexipyridines;
triazacyclosexipyridines; diazacyclosexiquinolines;
triazacyclosexiquinolines; diazacyclosexipyrazines;
triazacyclosexipyrazines; diazacyclosexipyridazines;
triazacyclosexipyridazines; diazacyclosexipyrimidines;
triazacyclosexipyrimidines; diazacyclosexitriazines; and
triazacyclosexitriazines. N Valence Stabilizer #17c: Examples of
eight-membered macrocyclics, macrobicyclics, and macropolycyclics
(including catapinands, cryptands, cyclidenes, and sepulchrates)
wherein all eight binding sites are composed of nitrogen and are
contained in a combination of 6-membered heterocyclic rings and
amine or imine groups (N--N Tridentates, N--N Tetradentates, or
N--N Hexadentates) that meet the requirements for use as "wide
band" valence stabilizers for Co.sup.+3 include, but are not
limited to: diazacyclooctapyridines; tetraazacyclooctapyridines;
diazacyclooctaquinolines; tetraazacyclooctaquinolines;
diazacyclooctapyrazines; tetraazacyclooctapyrazines;
diazacyclooctapyridazines; tetraazacyclooctapyridazines;
diazacyclooctapyrimidines; tetraazacyclooctapyrimidines;
diazacyclooctatriazines; and tetraazacyclooctatriazines. N Valence
Stabilizer #17d: Examples of ten-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all ten binding
sites are composed of nitrogen and are contained in a combination
of 6-membered heterocyclic rings and amine or imine groups (N--N
Tridentates, N--N Tetradentates, or N--N Hexadentates) that meet
the requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to: diazacyclodecapyridines;
pentaazacyclodecapyridines; diazacyclodecaquinolines;
pentaazacyclodecaquinolines; diazacyclodecapyrazines;
pentaazacyclodecapyrazines; diazacyclodecapyridazines;
pentaazacyclodecapyridazines; diazacyclodecapyrimidines;
pentaazacyclodecapyrimidines; diazacyclodecatriazines; and
pentaazacyclodecatriazines. N Valence Stabilizer #18: Examples of
amidines and diamidines (N--N bidentates or N--N Tetradentates)
that meet the requirements for use as "wide band" valence
stabilizers for Co.sup.+3 include, but are not limited to:
N,N'-dimethylformamidine; N,N'-diethylformamidine;
N,N'-diisopropylformamidine; N,N'-dibutylformamidine;
N,N'-diphenylformamidine; N,N'-dibenzylformamidine;
N,N'-dinaphthylformamidine; N,N'-dicyclohexylformamidine;
N,N'-dinorbornylformamidine; N,N'-diadamantylformamidine;
N,N'-dianthraquinonylformamidine; N,N'-dimethylacetamidine;
N,N'-diethylacetamidine; N,N'-diisopropylacetamidine;
N,N'-dibutylacetamidine; N,N'-diphenylacetamidine;
N,N'-dibenzylacetamidine; N,N'-dinaphthylacetamidine;
N,N'-dicyclohexylacetamidine; N,N'-dinorbornylacetamidine;
N,N'-diadamantylacetamidine; N,N'-dimethylbenzamidine;
N,N'-diethylbenzamidine; N,N'-diisopropylbenzamidine;
N,N'-dibutylbenzamidine; N,N'-diphenylbenzamidine;
N,N'-dibenzylbenzamidine; N,N'-dinaphthylbenzamidine;
N,N'-dicyclohexylbenzamidine; N,N'-dinorbornylbenzamidine;
N,N'-diadamantylbenzamidine; N,N'-dimethyltoluamidine;
N,N'-diethyltoluamidine; N,N'-diisopropyltoluamidine;
N,N'-dibutyltoluamidine; N,N'-diphenyltoluamidine;
N,N'-dibenzyltoluamidine; N,N'-dinaphthyltoluamidine;
N,N'-dicyclohexyltoluamidine; N,N'-dinorbornyltoluamidine;
N,N'-diadamantyltoluamidine; oxalic diamidine; malonic diamidine;
succinic diamidine; glutaric diamidine; adipic diamidine; pimelic
diamidine; suberic diamidine; phthalic diamidine; terephthalic
diamidine; isophthalic diamidine; piperazine diamidine;
2-iminopyrrolidine; 2-iminopiperidine; amidinobenzamide;
benzamidine; chloroazodin; and debrisoquin. N Valence Stabilizer
#19: Examples ofbiguamides (imidodicarbonimidic diamides),
biguanidines, imidotricarbonimidic diamides, imidotetracarbonimidic
diamides, dibiguamides, bis(biguanidines), polybiguamides, and
poly(biguanidines) (N--N bidentates, N--N tridentates, N--N
tetradentates, and N--N hexadentates) that meet the requirements
for use as "wide band" valence stabilizers for Co.sup.+3 include,
but are not limited to: biguamide (bigH); biguanidine,
methylbiguamide; ethylbiguamide; isopropylbiguamide;
butylbiguamide; benzylbiguamide; phenylbiguamide; tolylbiguamide;
naphthylbiguamide; cyclohexylbiguamide; norbornylbiguamide;
adamantylbiguamide; dimethylbiguamide; diethylbiguamide;
diisopropylbiguamide; dibutylbiguamide; dibenzylbiguamide;
diphenylbiguamide; ditolylbiguamide; dinaphthylbiguamide;
dicyclohexylbiguamide; dinorbornylbiguamide; diadamantylbiguamide;
ethylenedibiguamide; propylenedibiguamide;
tetramethylenedibiguamide; pentamethylenedibiguamide;
hexamethylenedibiguamide; heptamethylenedibiguamide;
octamethylenedibiguamide; phenylenedibiguamide;
piperazinedibiguamide; oxalyldibiguamide; malonyldibiguamide;
succinyldibiguamide; glutaryldibiguamide; adipyldibiguamide;
pimelyldibiguamide; suberyldibiguamide; phthalyldibiguamide;
paludrine; polyhexamethylene biguamide; 2-guanidinothiazole;
2-guanidinooxazole; 2-guanidinoimidazole; 3-guanidinopyrazole;
3-guanidino-1,2,4-triazole; 5-guanidinotetrazole; alexidine;
buformin; and moroxydine. N Valence Stabilizer #20: Examples of
diamidinomethanes, bis(diamidinomethanes), and
poly(diamidinomethanes) (N--N bidentates, N--N tridentates, N--N
tetradentates, and N--N hexadentates) that meet the requirements
for use as "wide band" valence stabilizers for Co.sup.+3 include,
but are not limited to: diamidinomethane; N-methyldiamidinomethane;
N-ethyldiamidinomethane; N-isopropyldiamidinomethane;
N-butyldiamidinomethane; N-benzyldiamidinomethane;
N-phenyldiamidinomethane; N-tolyldiamidinomethane;
N-naphthyldiamidinomethane; N-cyclohexyldiamidinomethane;
N-norbornyldiamidinomethane; N-adamantyldiamidinomethane;
dimethyldiamidinomethane; diethyldiamidinomethane;
diisopropyldiamidinomethane; dibutyldiamidinomethane;
dibenzyldiamidinomethane; diphenyldiamidinomethane;
ditolyldiamidinomethane; dinaphthyldiamidinomethane;
dicyclohexyldiamidinomethane; dinorbornyldiamidinomethane;
diadamantyldiamidinomethane; ethylenebisdiamidinomethane;
propylenebisdiamidinomethane; tetramethylenebisdiamidinomethane;
pentamethylenebisdiamidinomethane;
hexamethylenebisdiamidinomethane;
heptamethylenebisdiamidinomethane;
octamethylenebisdiamidinomethane; phenylenebisdiamidinomethane;
piperazinebisdiamidinomethane; oxalylbisdiamidinomethane;
malonylbisdiamidinomethane; succinylbisdiamidinomethane;
glutarylbisdiamidinomethane; phthalylbisdiamidinomethane;
2-amidinomethylthiazole; 2-amidinomethyloxazole;
2-amidinomethylimidazole; 3-amidinomethylpyrazole;
3-amidinomethyl-1,2,4-triazole; and 5-amidinomethyltetrazole. N
Valence Stabilizer #21: Examples of imidoylguanidines,
amidinoguanidines, bis(imidoylguanidines), bis(amidinoguanidines),
poly(imidoylguanidines), and poly(amidinoguanidines) (N--N
bidentates, N--N tridentates, N--N tetradentates, and N--N
hexadentates) that meet the requirements for use as "wide band"
valence stabilizers for Co.sup.+3 include, but are not
limited to: acetimidoylguanidine; amidinoguanidine,
benzimidoylguanidine; cyclohexylimidoylguanidine;
pentafluorobenzimidoylguanidine; 2-N-imidoylaminothiazole;
2-N-imidoylaminooxazole; 2-N-imidoylaminoimidazole;
3-N-imidoylaminopyrazole; 3-N-imidoylamino-1,2,4-triazole; and
5-N-imidoylaminotetrazole. N Valence Stabilizer #22: Examples of
diformamidine oxides (dicarbonimidic diamides), tricarbonimidic
diamides, tetracarbonimidic diamides, bis(diformamidine oxides),
and poly(diformamidine oxides) (N--N bidentates, N--N tridentates,
or N--N tetradentates) that meet the requirements for use as "wide
band" valence stabilizers for Co.sup.+3 include, but are not
limited to: diformamidine oxide; methyldiformamidine oxide;
ethyldiformamidine oxide; isopropyldiformamidine oxide;
butyldiformamidine oxide; benzyldiformamidine oxide;
phenyldiformamidine oxide; tolyldiformamidine oxide;
naphthyldiformamidine oxide; cyclohexyldiformamidine oxide;
norbornyldiformamidine oxide; adamantyldiformamidine oxide;
dimethyldiformamidine oxide; diethyldiformamidine oxide;
diisopropyldiformamidine oxide; dibutyldiformamidine oxide;
dibenzyldiformamidine oxide; diphenyldiformamidine oxide;
ditolyldiformamidine oxide; dinaphthyldiformamidine oxide;
dicyclohexyldiformamidine oxide; dinorbornyldiformamidine oxide;
diadamantyldiformamidine oxide; 2-O-amidinohydroxythiazole;
2-O-amidinohydroxyoxazole; 2-O-amidinohydroxyimidazole;
3-O-amidinohydroxypyrazole; 3-O-amidinohydroxy-1,2,4-triazole; and
5-O-amidinohydroxytetrazole. N Valence Stabilizer #23: Examples of
diformamidine sulfides (thiodicarbonimidic diamides),
thiotricarbonimidic diamides, thiotetracarbonimidic diamides,
bis(diformamidine sulfides), and poly(diformamidine sulfides) (N--N
bidentates, N--N tridentates, or N--N tetradentates) that meet the
requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to: diformamidine sulfide;
methyldiformamidine sulfide; ethyldiformamidine sulfide;
isopropyldiformamidine sulfide; butyldiformamidine sulfide;
benzyldiformamidine sulfide; phenyldiformamidine sulfide;
tolyldiformamidine sulfide; naphthyldiformamidine sulfide;
cyclohexyldiformamidine sulfide; norbornyldiformamidine sulfide;
adamantyldiformamidine sulfide; dimethyldiformamidine sulfide;
diethyldiformamidine sulfide; diisopropyldiformamidine sulfide;
dibutyldiformamidine sulfide; dibenzyldiformamidine sulfide;
diphenyldiformamidine sulfide; ditolyldiformamidine sulfide;
dinaphthyldiformamidine sulfide; dicyclohexyldiformamidine sulfide;
dinorbornyldiformamidine sulfide; diadamantyldiformamidine sulfide;
phenylthiobisformamidine; 2-S-amidinomercaptothiazole;
2-S-amidinomercaptooxazole; 2-S-amidinomercaptoimidazole;
3-S-amidinomercaptopyrazole; 3-S-amidinomercapto-1,2,4-triazole;
and 5-S-amidinomercaptotetrazole. N Valence Stabilizer #24:
Examples of imidodicarbonimidic acids, diimidodicarbonimidic acids,
imidotricarbonimidic acids, imidotetracarbonimidic acids, and
derivatives thereof(N--N Bidentates, N--N Tridentates, N--N
Tetradentates, and N--N Hexadentates) that meet the requirements
for use as "wide band" valence stabilizers for Co.sup.+3 include,
but are not limited to: imidodicarbonimidic acid,
diimidodicarbonimidic acid, imidotricarbonimidic acid,
imidotetracarbonimidic acid; O-methylimidodicarbonimidic acid;
O-ethylimidodicarbonimidic acid; O-isopropylimidodicarbonimidic
acid; O-phenylimidodicarbonimidic acid; O-benzylimidodicarbonimidic
acid; O-cyclohexylimidodicarbonimidic acid;
O-naphthylimidodicarbonimidic acid; O-norbornylimidodicarbonimidic
acid; O-adamantylimidodicarbonimidic acid;
O,O'-dimethylimidodicarbonimidic acid;
O,O'-diethylimidodicarbonimidic acid;
O,O'-diisopropylimidodicarbonimidic acid;
O,O'-diphenylimidodicarbonimidic acid;
O,O'-dibenzylimidodicarbonimidic acid;
O,O'-dicyclohexylimidodicarbonimidic acid;
O,O'-dinaphthylimidodicarbonimidic acid;
O,O'-dinorbornylimidodicarbonimidic acid; and
O,O'-diadamantylimidodicarbonimidic acid. N Valence Stabilizer #25:
Examples ofthioimidodicarbonimidic acids, thiodiimidodicarbonimidic
acids, thioimidotricarbonimidic acids, thioimidotetracarbonimidic
acids, and derivatives thereof (N--N Bidentates, N--N Tridentates,
N--N Tetradentates, and N--N Hexadentates) that meet the
requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to: thioimidodicarbonimidic
acid, thiodiimidodicarbonimidic acid, thioimidotricarbonimidic
acid, thioimidotetracarbonimidic acid;
O-methylthioimidodicarbonimidic acid;
O-ethylthioimidodicarbonimidic acid;
O-isopropylthioimidodicarbonimidic acid;
O-phenylthioimidodicarbonimidic acid;
O-benzylthioimidodicarbonimidic acid;
O-cyclohexylthioimidodicarbonimidic acid;
O-naphthylthioimidodicarbonimidic acid;
O-norbornylthioimidodicarbonimidic acid;
O-adamantylthioimidodicarbonimidic acid;
O,O'-dimethylthioimidodicarbonimidic acid;
O,O'-diethylthioimidodicarbonimidic acid;
O,O'-diisopropylthioimidodicarbonimidic acid;
O,O'-diphenylthioimidodicarbonimidic acid;
O,O'-dibenzylthioimidodicarbonimidic acid;
O,O'-dicyclohexylthioimidodicarbonimidic acid;
O,O'-dinaphthylthioimidodicarbonimidic acid;
O,O'-dinorbornylthioimidodicarbonimidic acid; and
O,O'-diadamantylthioimidodicarbonimidic acid. N Valence Stabilizer
#26: Examples of diumidoylimines, diimidoylhydrazides,
bis(diimidoylimines), bis(diimidoylhydrazides),
poly(diimidoylimines), and poly(diimidoylhydrazides) (N--N
Tridentates and N--N Hexadentates) that meet the requirements for
use as "wide band" valence stabilizers for Co.sup.+3 include, but
are not limited to: diacetimidoylimine; dibenzimidoylimine; and
dicyclohexylimidoylimine. N Valence Stabilizer #27: Examples
ofimidosulfamides, diimidosulfamides, bis(imidosulfamides),
bis(diimidosulfamides), poly(imidosulfamides), and
poly(diimidosulfamides) (N--N Bidentates, N--N Tridentates, N--N
Tetradentates, and N--N Hexadentates) that meet the requirements
for use as "wide band" valence stabilizers for Co.sup.+3 include,
but are not limited to: imidosulfamidic acid, duimidosulfamidic
acid; O-phenylimidosulfamide; O-benzylimidosulfamide;
N-phenylimidosulfamide; N-benzylimidosulfamide;
O-phenyldiimidosulfamide; O-benzyldiimidosulfamide;
N-phenyldiimidosulfamide; and N-benzyldiimidosulfamide. N Valence
Stabilizer #28: Examples of phosphoramidimidic triamides,
bis(phosphoramidimidic triamides), and poly(phosphoramidimidic
triamides) and derivatives thereof (N--N Bidentates, N--N
Tridentates, N--N Tetradentates, and N--N Hexadentates) that meet
the requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to: phosphoramidimidic
triamide; N-phenylphosphoramidimidic triamide;
N-benzylphosphoramidimidic triamide; N-naphthylphosphoramidimidic
triamide; N-cyclohexylphosphoramidimidic triamide;
N-norbornylphosphoramidimidic triamide;
N,N'-diphenylphosphoramidimidic triamide;
N,N'-dibenzylphosphoramidimidic triamide;
N,N'-dinaphthylphosphoramidimidic triamide;
N,N'-dicyclohexylphosphoramidimidic triamide; and
N,N'-dinorbornylphosphoramidimidic triamide. N Valence Stabilizer
#29: Examples of phosphoramidimidic acid, phosphorodiamidimidic
acid, bis(phosphoramidimidic acid), bis(phosphorodiamidimidic
acid), poly(phosphoramidimidic acid), poly(phosphorodiamidimidic
acid), and derivatives thereof (N--N Bidentates, N--N Tridentates,
N--N Tetradentates, and N--N Hexadentates) that meet the
requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to: phosphoramidimidic acid,
phosphorodiamidimidic acid, O-phenylphosphoramidimidic acid;
O-benzylphosphoramidimidic acid; O-naphthylphosphoramidimidic acid;
O-cyclohexylphosphoramidimidic acid; O-norbornylphosphoramidimidic
acid; O,O'-diphenylphosphoramidimidic acid;
O,O'-dibenzylphosphoramidimidic acid;
O,O'-dinaphthylphosphoramidimidic acid;
O,O'-dicyclohexylphosphoramidimidic acid; and
O,O'-dinorbornylphosphoramidimidic acid. N Valence Stabilizer #30:
Examples of phosphoramidimidodithioic acid,
phosphorodiamidimidothioic acid, bis(phosphoramidimidodithioic
acid), bis(phosphorodiamidimidothioic acid),
poly(phosphoramidimidodithioic acid),
poly(phosphorodiamidimidothioic acid), and derivatives thereof(N--N
Bidentates, N--N Tridentates, N--N Tetradentates, and N--N
Hexadentates) that meet the requirements for use as "wide band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
phosphoramidimidodithioic acid, phosphorodiamidimidothioic acid,
S-phenylphosphoramidimidodithioic acid;
S-benzylphosphoramidimidodithoic acid;
S-naphthylphosphoramidimidodithioic acid;
S-cyclohexylphosphoramidimidodithioic acid;
S-norbornylphosphoramidimidodithioic acid;
S,S'-diphenylphosphoramidimidodithioic acid;
S,S'-dibenzylphosphoramidimidodithioic acid;
S,S'-dinaphthylphosphoramidimidodithioic acid;
S,S'-dicyclohexylphosphoramidimidodithioic acid; and
S,S'-dinorbornylphosphoramidimidodithioic acid. N Valence
Stabilizer #31: Examples of azo compounds with amino, imino, oximo,
diazeno, or hydrazido substitution at the ortho- (for aryl) or
alpha- or beta- (for alkyl) positions, bis[o-(H.sub.2N--) or alpha-
or beta-(H.sub.2N--)azo compounds], or poly[o-(H.sub.2N--) or
alpha- or beta-(H.sub.2N--)azo compounds) (N--N Bidentates, N--N
Tridentates, N--N Tetradentates, or N--N Hexadentates) that meet
the requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to: o-aminoazobenzene;
o,o'-diaminoazobenzene; (2-pyridine)azobenzene;
1-phenylazo-2-naphthylamine; pyridineazo-2-naphthol (PAN);
pyridineazoresorcinol (PAR);
o-hydroxy-o'-(beta-aminoethylamino)azobenzene; Benzopurpurin 4B;
Congo Red; Fat Brown RR; benzopurpurin; Congo Red; Direct Red 75;
Mordant Brown 48; Nitro Red; 2-imidazolylazobenzene;
2-benzimidazolylazobenzene; 3-pyrazolylazobenzene;
3-(1,2,4-triazolyl)azobenzene; 2-pyridylazobenzene;
2-pyrazinylazobenzene; and 2-pyrimidinylazobenzene. N Valence
Stabilizer #32: Examples of diazeneformimidamides
(diazeneamidines), diazeneacetimidamides
(diazene-alpha-amidinoalkanes(alkenes)),
bis(diazeneformimidamides), bis(diazeneacetimidamides),
poly(diazeneformimidamides), and poly(diazeneacetimidamides) (N--N
Bidentates, N--N Tetradentates, and N--N Hexadentates) that meet
the requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to: diazeneformimidamide
(diazeneamidine); diazeneacetimidamide
(diazene-alpha-amidinomethane); phenyldiazeneformimidamide;
triphenyldiazeneformimidamide; phenyldiazeneacetimidamide; and
triphenyldiazeneacetimidamide. N Valence Stabilizer #33: Examples
of diazeneformimidic acid, diazeneacetimidic acid,
bis(diazeneformimidic acid), bis(diazeneacetimidic acid),
poly(diazeneformimidic acid), poly(diazeneacetimidic acid), and
derivatives thereof(N--N Bidentates, N--N Tetradentates, and N--N
Hexadentates) that meet the requirements for use as "wide band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
diazeneformimidic acid, diazeneacetimidic acid,
phenyldiazeneformimidic acid, diphenyldiazeneformimidic acid,
phenyldiazeneacetimidic acid, and diphenyldiazeneacetimidic acid. N
Valence Stabilizer #34: Examples of diazeneformimidothioic acid,
diazeneacetimidothioic acid, bis(diazeneformimidothioic acid),
bis(diazeneacetimidothioic acid), poly(diazeneformimidothioic
acid), poly(diazeneacetimidothioic acid), and derivatives thereof
(N--N Bidentates, N--N Tetradentates, and N--N Hexadentates) that
meet the requirements for use as "wide band" valence stabilizers
for Co.sup.+3 include, but are not limited to:
diazeneformimidothioic acid, diazeneacetimidothioic acid,
phenyldiazeneformimidothioic acid, diphenyldiazeneformimidoihioic
acid, phenyldiazeneacetimidothioic acid, and
diphenyldiazeneacetimidothioic acid. N Valence Stabilizer #35:
Examples of imidoyldiazenes, bis(imidoyldiazenes), and
poly(imidoyldiazenes), (N--N Tridentates and N--N Hexadentates)
that meet the requirements for use as "wide band" valence
stabilizers for Co .sup.3 include, but are not limited to:
acetimidoyldiazene; benzimidoyldiazene; and
cyclohexylimidoyldiazene. N Valence Stabilizer #36: Examples of
diazenediformimidamides (1,2-diazenediamidines),
diazenediacetimidamides
(1,2-diazene-di-alpha-amidinoalkanes(alkenes)),
bis(diazenediformimidamides), bis(diazenediacetimidamides),
poly(diazenediformimidamides), and poly(diazenediacetimidamides)
(N--N Tridentates and N--N Hexadentates) that meet the requirements
for use as "wide band" valence stabilizers for Co.sup.+3 include,
but are not limited to: diazenediformimidamide
(1,2-diazenediamidine), diazenediacetimidamide
(1,2-diazene-di-alpha-amidinomethane);
diphenyldiazenediformimidamide; tetraphenyldiazenediformimidamide;
diphenyldiazenediacetimidamide; and
tetraphenyldiazenediacetimidamide. N Valence Stabilizer #37:
Examples of diazenediformimidic acid, diazenediacetimidic acid,
bis(diazenediformimidic acid), bis(diazenediacetimidic acid),
poly(diazenediformimidic acid), and poly(diazenediacetimidic acid),
and derivatives thereof (N--N Tridentates and N--N Hexadentates)
that meet the requirements for use as "wide band" valence
stabilizers for Co.sup.+3 include, but are not limited to:
diazenediformimidic acid, diazenediacetimidic acid,
diphenyldiazenediformimidic acid, and diphenyldiazenediacetimidic
acid. N Valence Stabilizer #38: Examples of
diazenediformimidothioic acid, diazenediacetimidothioic acid,
bis(diazenediformimidothioic acid), bis(diazenediacetimidothioic
acid), poly(diazenediformimidothioic acid), and
poly(diazenediacetimidothioic acid), and derivatives thereof(N--N
Tridentates and N--N Hexadentates) that meet the requirements for
use as "wide band" valence stabilizers for Co.sup.+3 include, but
are not limited to: diazenediformimidothioic acid,
diazenediacetimidothioic acid, diphenyldiazenediformimidothioic
acid, and diphenyldiazenediacetimidothioic acid. N Valence
Stabilizer #39: Examples of diimidoyldiazenes,
bis(diimidoyldiazenes), and poly(diimidoyldiazenes), (N--N
Tridentates and N--N Hexadentates) that meet the requirements for
use as "wide band" valence stabilizers for Co.sup.+3 include, but
are not limited to: diacetimidoyldiazene; dibenzimidoyldiazene; and
dicyclohexylimidoyldiazene. N Valence Stabilizer #40: Examples of
ortho-amino (or -hydrazido) substituted formazans, bis(o-amino or
-hydrazido substituted formazans), and poly(o-amino or -hydrazido
substituted formazans) (N--N Bidentates, N--N Tridentates, N--N
Tetradentates, and N--N Hexadentates) that meet the requirements
for use as "wide band" valence stabilizers for Co.sup.+3 include,
but are not limited to: 1-(2-aminophenyl)-3,5-diphenylformazan; and
1,5-bis(2-aminophenyl)-3-phenylformazan. N Valence Stabilizer #41:
Examples of ortho-amino (or -hydrazido) substituted azines
(including ketazines), bis(o-amino or hydrazido substituted
azines), and poly(o-amino or hydrazido substituted azines) (N--N
Bidentates, N--N Tridentates, N--N Tetradentates, and N--N
Hexadentates) that meet the requirements for use as "wide band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
2-amino-1-benzalazine; 2-amino-1-naphthalazine; and
2-amino-1-cyclohexanonazine. N Valence Stabilizer #42: Examples of
Schiff Bases with one Imine (C.dbd.N) Group and with ortho- or
alpha- or beta-amino or imino or oximo or diazeno or hydrazido
substitution (N--N Bidentates, N--N Tridentates, N--N
Tetradentates, N--N Pentadentates, or N--N Hexadentates) that meet
the requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to:
N-(2-Aminobenzaldehydo)isopropylamine;
N-(2-Pyridinecarboxaldehydo)isopropylamine;
N-(2-Pyrrolecarboxaldehydo)isopropylamine;
N-(2-Acetylpyridino)isopropylamine;
N-(2-Acetylpyrrolo)isopropylamine;
N-(2-Aminoacetophenono)isopropylamine;
N-(2-Aminobenzaldehydo)cyclohexylamine;
N-(2-Pyridinecarboxaldehydo)cyclohexylamine;
N-(2-Pyrrolecarboxaldehydo)cyclohexylamine;
N-(2-Acetylpyridino)cyclohexylamine;
N-(2-Acetylpyrrolo)cyclohexylamine;
N-(2-Aminoacetophenono)cyclohexylamine;
N-(2-Aminobenzaldehydo)aniline;
N-(2-Pyridinecarboxaldehydo)aniline;
N-(2-Pyrrolecarboxaldehydo)aniline; N-(2-Acetylpyridino)aniline;
N-(2-Acetylpyrrolo)aniline; N-(2-Aminoacetophenono)aniline;
N-(2-Aminobenzaldehydo)aminonorbornane;
N-(2-Pyridinecarboxaldehydo)aminonorbornane;
N-(2-Pyrrolecarboxaldehydo)aminonorbornane;
N-(2-Acetylpyridino)aminonorbornane;
N-(2-Acetylpyrrolo)aminonorbornane;
N-(2-Aminoacetophenono)aminonorbornane; 2-pyrrolecarboxaldehyde
phenylhydrazone; 2-pyrrolecarboxaldehyde 2-pyridyl hydrazone;
2-aminobenzaldehyde phenylhydrazone (nitrin); and
2-aminobenzaldehyde 2-pyridyl hydrazone. Also includes hydrazones
with ortho-N substitution. N Valence Stabilizer #43: Examples of
Schiff Bases with two Imine (C.dbd.N) Groups and without ortho-
(for aryl constituents) or alpha- or beta- (for alkyl constituents)
hydroxy, carboxy, carbonyl, thiol, mercapto, thiocarbonyl, amino,
imino, oximo, diazeno, or hydrazido substitution (N--N Bidentates)
that meet the requirements for use as "wide band" valence
stabilizers for Co.sup.+3 include, but are not limited to:
N,N'-(Glyoxalo)diisopropylamine; N,N'-(Glyoxalo)dicyclohexylamine;
N,N'-(Glyoxalo)dianiline; N,N'-(Glyoxalo)di-aminonorbornane;
N,N'-(Malondialdehydo)diisopropylamine;
N,N'-(Malondialdehydo)dicyclohexylamine;
N,N'-(Malondialdehydo)dianiline;
N,N'-(Malondialdehydo)di-aminonorbornane;
N,N'-(Phthalicdialdehydo)diisopropylamine;
N,N'-(Phthalicdialdehydo)dicyclohexylamine;
N,N'-(Phthalicdialdehydo)dianiline;
N,N'-(Phthalicdialdehydo)di-aminonorbornane;
N,N'-(Formylcamphoro)diisopropylamine;
N,N'-(Formylcamphoro)dicyclohexylamine;
N,N'-(Formylcamphoro)dianiline;
N,N'-(Formylcamphoro)di-aminonorbornane;
N,N'-(Acetylacetonato)diisopropylamine;
N,N'-(Acetylacetonato)dicyclohexylamine;
N,N'-(Acetylacetonato)dianiline;
N,N'-(Acetylacetonato)di-aminonorbornane;
N,N'-(Diacetylbenzeno)diisopropylamine;
N,N'-(Diacetylbenzeno)dicyclohexylamine;
N,N'-(Diacetylbenzeno)dianiline;
N,N'-(Diacetylbenzeno)di-aminonorbornane;
N,N'-(1,2-Cyclohexanono)diisopropylamine;
N,N'-(1,2-Cyclohexanono)dicyclohexylamine;
N,N'-(1,2-Cyclohexanono)dianiline;
N,N'-(1,2-Cyclohexanono)di-aminonorbornane;
N,N'-(Camphorquinono)diisopropylamine;
N,N'-(Camphorquinono)dicyclohexylamine;
N,N'-(Camphorquinono)dianiline;
N,N'-(Camphorquinono)di-aminonorbornane;
N,N'-(Benzaldehydo)ethylenediamine;
N,N'-(Naphthaldehydo)ethylenediamine;
N,N'-(Acetophenono)ethylenediamine;
N,N'-(Benzaldehydo)trimethylenediamine;
N,N'-(Naphthaldehydo)trimethylenediamine;
N,N'-(Acetophenono)trimethylenediamine;
N,N'-(Benzaldehydo)cyclohexane-1,2-diamine;
N,N'-(Naphthaldehydo)cyclohexane-1,2-diamine;
N,N'-(Acetophenono)cyclohexane-1,2-diamine;
N,N'-(Benzaldehydo)-1,2-diaminobenzene;
N,N'-(Naphthaldehydo)-1,2-diaminobenzene;
N,N'-(Acetophenono)-1,2-diaminobenzene;
N,N'-(Acetylacetonato)ethylenediamine;
N,N'-(Acetylacetonato)-1,2-cyclohexylenediamine;
N,N'-(Acetylacetonato)-1,2-propylenediamine;
N,N'-(Glyoxalo)-o-phenylenediamine; and
N,N'-(Glyoxalo)ethylenediamine. Also includes dihydrazones. N
Valence Stabilizer #44: Examples of SchiffBases with two Imine
(C.dbd.N) Groups and with ortho- or alpha- or beta-amino or imino
or oximo or diazeno or hydrazido substitution (N--N Bidentates,
N--N Tridentates, N--N Tetradentates, N--N Pentadentates, or N--N
Hexadentates) that meet the requirements for use as "wide band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
N,N'-(2,6-Pyridinedicarboxaldehydo)diisopropylamine;
N,N'-(2,6-Pyridinedicarboxaldehydo)dicyclohexylamine;
N,N'-(2,6-Pyridinedicarboxaldehydo)dianiline;
N,N'-(2,6-Pyridinedicarboxaldehydo)di-aminonorbornane;
N,N'-(2,5-Pyrroledicarboxaldehydo)diisopropylamine;
N,N'-(2,5-Pyrroledicarboxaldehydo)dicyclohexylamine;
N,N'-(2,5-Pyrroledicarboxaldehydo)dianiline;
N,N'-(2,5-Pyrroledicarboxaldehydo)di-aminonorbornane;
N,N'-(o-Aminophthalicdialdehydo) diisopropyl amine;
N,N'-(o-Aminophthalicdialdehydo)dicyclohexylamine;
N,N'-(o-Aminophthalicdialdehydo)dianiline;
N,N'-(o-Aminophthalicdialdehydo)di-aminonorbornane;
N,N'-(o-Aminoformylcamphoro)diisopropylamine;
N,N'-(o-Aminoformylcamphoro)dicyclohexylamine;
N,N'-(o-Aminoformylcamphoro)dianiline;
N,N'-(o-Aminoformylcamphoro)di-aminonorbornane;
N,N'-(2,6-Diacetylpyridino)diisopropylamine;
N,N'-(2,6-Diacetylpyridino)dicyclohexylamine;
N,N'-(2,6-Diacetylpyridino)di aniline;
N,N'-(2,6-Diacetylpyridino)di-aminonorbornane; N,N'-(o
-Aminodiacetylbenzeno)diisopropylamine;
N,N'-(o-Aminodiacetylbenzeno)dicyclohexylamine;
N,N'-(o-Aminodiacetylbenzeno)dianiline;
N,N'-(o-Aminodiacetylbenzeno)di-aminonorbornane;
N,N'-(3,6-Diamino-1,2-cyclohexanono)diisopropylamine;
N,N'-(3,6-Diamino-1,2-cyclohexanono)dicyclohexylamine;
N,N'-(3,6-Diamino-1,2-cyclohexanono)dianiline;
N,N'-(3,6-Diamino-1,2-cyclohexanono)di-aminonorbornane;
N,N'-(2,5-Diacetylpyrrolo)diisopropylamine;
N,N'-(2,5-Diacetylpyrrolo)dicyclohexylamine;
N,N'-(2,5-Diacetylpyrrolo)dianiline;
N,N'-(2,5-Diacetylpyrrolo)di-aminonorbornane;
N,N'-(o-Aminobenzaldehydo)ethylenediamine;
N,N'-(o-Aminonaphthaldehydo)ethylenediamine;
N,N'-(o-Aminoacetophenono)ethylenediamine;
N,N'-(o-Aminobenzaldehydo)trimethylenediamine;
N,N'-(o-Aminonaphthaldehydo)trimethylenediamine;
N,N'-(o-Aminoacetophenono)trimethylenediamine;
N,N'-(o-Aminobenzaldehydo)cyclohexane-1,2-diamine;
N,N'-(o-Aminonaphthaldehydo)cyclohexane-1,2-diamine;
N,N'-(o-Aminoacetophenono)cyclohexane-1,2-diamine; N,N
'-(o-Aminobenzaldehydo)-1,2-diaminobenzene;
N,N'-(o-Aminonaphthaldehydo)-1,2-diaminobenzene; and
N,N'-(o-Aminoacetophenono)-1,2-diaminobenzene. Also includes
hydrazones with ortho-N substitution. N Valence Stabilizer #45:
Examples of SchiffBases with three Imine (C.dbd.N) Groups and
without ortho- (for aryl constituents) or alpha- or beta- (for
alkyl constituents) hydroxy, carboxy, carbonyl, thiol, mercapto,
thiocarbonyl, amino, imino, oximo, diazeno, or hydrazido
substitution (N--N Tridentates) that meet the requirements for use
as "wide band" valence stabilizers for Co.sup.+3 include, but are
not limited to: N,N',N''-(Benzaldehydo)tris(2-aminoethyl)amine;
N,N',N''-(Naphthaldehydo)tris(2-aminoethyl)amine; and
N,N',N''-(Acetophenono)tris(2-aminoethyl)amine. Also includes
trihydrazones. N Valence Stabilizer #46: Examples of SchiffBases
with three Imine (C.dbd.N) Groups and with ortho- or alpha- or
beta-amino or imino or oximo or diazeno or hydrazido substitution
(N--N Tridentates, N--N Tetradentates, N--N Pentadentates, or N--N
Hexadentates) that meet the requirements for use as "wide band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
N,N',N''-(o-Aminobenzaldehydo)tris(2-aminoethyl)amine;
N,N',N''-(o-Aminonaphthaldehydo)tris(2-aminoethyl)amine; and
N,N',N''-(o-Aminoacetophenono)tris(2-aminoethyl)amine. S Valence
Stabilizer #1: Examples of macrocyclic, macrobicyclic, and
macropolycyclic oligothioketones (including catapinands, cryptands,
cyclidenes, and sepulchrates) wherein all binding sites are
composed of thioketones (especially in the beta position) (S--S
Bidentates, S--S Tetradentates, and S--S Hexadentates) that meet
the requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to:
hexathioketocyclotetracosane ([24]ane(.dbd.S).sub.6);
hexathioketocycloheneicosane ([21]ane(.dbd.S).sub.6);
hexathioketocyclooctadecane ([18]ane(.dbd.S).sub.6);
hexathioketocyclopentadecane ([15]ane(.dbd.S).sub.6);
tetrathioketocycloeicosane ([20]ane(.dbd.S).sub.4);
tetrathioketocyclooctadecane ([18]ane(.dbd.S).sub.4);
tetrathioketocyclohexadecane ([16]ane(.dbd.S).sub.4);
tetrathioketocyclotetradecane ([14]ane(.dbd.S).sub.4);
tetrathioketocyclododecane ([12]ane(.dbd.S).sub.4);
dithioketocyclohexadecane ([16]ane(.dbd.S).sub.2);
dithioketocyclotetraadecane ([14]ane(.dbd.S).sub.2);
dithioketocyclododecane ([12]ane(.dbd.S).sub.2);
dithioketocyclodecane ([10]ane(.dbd.S).sub.2); and
dithioketocyclooctane ([8]ane(.dbd.S).sub.2). S Valence Stabilizer
#2: Examples of macrocyclic, macrobicyclic, and macropolycyclic
dithiolenes (including catapinands, cryptands, cyclidenes, and
sepulchrates) wherein all binding sites are composed of alpha-,
alpha-dithiolenes (meaning two thiol groups on a single carbon atom
in the ring) (S--S Bidentates, S--S Tetradentates, and S--S
Hexadentates) that meet the requirements for use as "wide band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
hexathiolocyclotetracosane ([24]ane(--SH).sub.6);
hexathiolocycloheneicosane ([21]ane(--SH).sub.6);
hexathiolocyclooctadecane ([18]ane(--SH).sub.6);
hexathiolocyclopentadecane ([15]ane(--SH).sub.6);
tetrathiolocycloeicosane ([20]ane(--SH).sub.4);
tetrathiolocyclooctadecane ([18]ane(--SH).sub.4);
tetrathiolocyclohexadecane ([16]ane(--SH).sub.4);
tetrathiolocyclotetradecane ([14]ane(--SH).sub.4);
tetrathiolocyclododecane ([12]ane(--SH).sub.4);
dithiolocyclohexadecane ([16]ane(--SH).sub.2);
dithiolocyclotetraadecane ([14]ane(--SH).sub.2);
dithiolocyclododecane ([12]ane(--SH).sub.2); dithiolocyclodecane
([10]ane(--SH).sub.2); and dithiolocyclooctane
([8]ane(--SH).sub.2). S Valence Stabilizer #3: Examples of
dithioimidodialdehydes, dithiohydrazidodialdehydes (thioacyl
thiohydrazides), bis(dithioimidodialdehydes),
bis(dithiohydrazidodialdehydes), poly(dithioimidodialdehydes), and
poly(dithiohydrazidodialdehydes) (S--S Bidentates, S--S
Tridentates, S--S Tetradentates) that meet the requirements for use
as "wide band" valence stabilizers for Co.sup.+3 include, but are
not limited to: dithiodiacetamide, dithiodipropanamide,
dithiodibutanamide, dithiodibenzamide, and dithiodicyclohexamide. S
Valence Stabilizer #4: Examples of dithioimidodicarbonic acids,
dithiohydrazidodicarbonic acids, bis(dithioimidodicarbonic acids),
bis(dithiohydrazidodicarbonic acids), poly(dithioimidodicarbonic
acids), poly(dithiohydrazidodicarbonic acids) and derivatives
thereof (S--S Bidentates, S--S Tridentates, S--S Tetradentates)
that meet the requirements for use as "wide band" valence
stabilizers for Co.sup.+3 include, but are not limited to:
dithioimidodicarbonic acid, dithiohydrazidodicarbonic acid,
O-phenyldithioimidodicarbonic acid, O-benzyldithioimidodicarbonic
acid, O-cyclohexyldithioimidodicarbonic acid,
O-norbornyldithioimidodicarbonic acid,
O,O'-diphenyldithioimidodicarbonic acid,
O,O'-dibenzyldithioimidodicarbonic acid,
O,O'-dicyclohexyldithioimidodicarbonic acid, and
O,O'-norbornyldithioimidodicarbonic acid. S Valence Stabilizer #5:
Examples of 1,3-dithioketones (dithio-beta-ketonates),
1,3,5-trithioketones, bis(1,3-dithioketones), and
poly(1,3-dithioketones) (S--S Bidentates, S--S Tridentates, S--S
Tetradentates) that meet the requirements for use as "wide band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
hexafluoropentanedithione; 1,3-diphenyl-1,3-propanedithione;
thiobenzoylthiopinacolone; dithiocyclohexoylmethane;
diphenylpentanetrithionate; tetramethylnonanetrithionate;
hexafluoroheptanetrithionate; trifluoroheptanetrithionate;
1-(2-thienyl)-1,3-butanedithione,
1-(2-naphthyl)-1,3-butanedithione, trifluorothioacetylthiocamphor;
and 1,3-indandithione. S Valence Stabilizer #6: Examples of
1,2-dithioketones (dithiolenes, dithio-alpha-ketonates),
1,2,3-trithioketones, dithiotropolonates, o-dithioquinones,
bis(1,2-dithioketones), and poly(1,2-dithioketones) (S--S
Bidentates, S--S Tridentates, S--S Tetradentates) that meet the
requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to: dithiotropolone;
1,2-dithiobenzoquinone (o-dithioquinone)(o-benzenedithiolate)(bdt);
di-tert-butyl-1,2-dithiobenzoquinone;
hexafluoro-1,2-dithiobenzoquinone; 1,2-dithionaphthoquinone;
9,10-dithiophenanthroquinone; ethylenedithiolene (edt);
maleonitriledithiolene (mnt); trifluoromethyldithiolene (tfd);
carbomethoxydithiolene (cmt); trithionedithiolene (dmit);
toluenedithiolate (tdt); dithiomanaldehyde
(propenethionethiolate)(ptt); dithioacetylacetonate (SacSac);
dijulolidinedithiolene; 2,3-piperazinedithiolate;
di(4-aminophenyl)dithiolene; dimercaptoisotrithione (dmit);
(4-octylphenyl)dithiolene; benzenetetrathiol; tetrathiosquaric
acid; trithiodeltic acid; pentathiocroconic acid; dithiocroconic
acid; hexathiorhodizonic acid; dithiorhodizonic acid;
ethylenetetrathiol; trans-butadienetetrathiolate; tetrathiooxalic
acid; 1,2-indandithione; naphthothioquinone;
acenapthenethioquinone; aceanthrenethioquinone; and
indole-2,3-dithione (thioisatin). S Valence Stabilizer #7: Examples
of dithiomalonamides (dithiomalonodiamides),
bis(dithiomalonamides), and polydithiomalonamides (S--S Bidentates,
S--S Tridentates, S--S Tetradentates) that meet the requirements
for use as "wide band" valence stabilizers for Co.sup.+3 include,
but are not limited to: dithiomalonamide, N-phenyldithiomalonamide,
N-benzyldithiomalonamide, N-pentafluorophenyldithiomalonamide,
N-cyclohexyldithiomalonamide, N-norbornyldithiomalonamide,
N,N'-diphenyldithiomalonamide, N,N'-dibenzyldithiomalonamide,
N,N'-dipentafluorophenyldithiomalonamide,
N,N'-dicyclohexyldithiomalonamide, and
N,N'-norbornyldithiomalonamide. S Valence Stabilizer #8: Examples
of2-thioacylthioacetamides, bis(2-thioacylthioacetamides), and
poly(2-thioacylthioacetamides) (S--S Bidentates, S--S Tridentates,
S--S Tetradentates) that meet the requirements for use as "wide
band" valence stabilizers for Co.sup.+3 include, but are not
limited to: 2-thioacetothioacetamide,
N-phenyl-2-thioacetothioacetamide,
N-pentafluorophenyl-2-thioacetothioacetamide,
N-benzyl-2-thioacetothioacetamide,
N-cyclohexyl-2-thioacetothioacetamide,
N-norbornyl-2-thioacetothioacetamide,
N-phenyl-2-thiobenzothioacetamide,
N-pentafluorophenyl-2-pentafluorothiobenzothioacetamide, and
N-cyclohexyl-2-thiocyclohexothioacetamide. S Valence Stabilizer #9:
Examples of dithioacyl sulfides, bis(dithioacyl sulfides), and
poly(dithioacyl sulfides), (S--S Bidentates, S--S Tridentates, S--S
Tetradentates) that meet the requirements for use as "wide band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
dithioacetyl sulfide; dithiopropanoyl sulfide; dithiobenzoyl
sulfide; and dithiopentafluorobenzoyl sulfide. S Valence Stabilizer
#10: Examples of trithiodicarbonic diamides, bis(trithiodicarbonic
diamides), and poly(trithiodicarbonic diamides) (S--S Bidentates,
S--S Tridentates, S--S Tetradentates) that meet the requirements
for use as "wide band" valence
stabilizers for Co.sup.+3 include, but are not limited to:
trithiodicarbonic diamide; N-phenyltrithiodicarbonic diamide;
N-pentafluorophenyltrithiodicarbonic diamide;
N-benzyltrithiodicarbonic diamide; N-cyclohexyltrithiodicarbonic
diamide; N-norbornyltrithiodicarbonic diamide;
N,N'-diphenyltrithiodicarbonic diamide;
N,N'-dipentafluorophenyltrithiodicarbonic diamide;
N,N'-dibenzyltrithiodicarbonic diamide;
N,N'-dicyclohexyltrithiodicarbonic diamide; and
N,N'-dinorbornyltrithiodicarbonic diamide. S Valence Stabilizer
#11: Examples of pentathio-, tetrathio-, or trithiodicarbonic
acids, bis(pentathio-, tetrathio-, or trithiodicarbonic acids),
poly(pentathio-, tetrathio-, or trithiodicarbonic acids), and
derivatives thereof (S--S Bidentates, S--S Tridentates, S--S
Tetradentates) that meet the requirements for use as "wide band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
pentathiodicarbonic acid, tetrathiodicarbonic acid,
trithiodicarbonic acid, O-phenyltrithiodicarbonic acid,
O-benzyltrithiodicarbonic acid, O-cyclohexyltrithiodicarbonic acid,
O-norbornyltrithiodicarbonic acid, O,O'-diphenyltrithiodicarbonic
acid, O,O'-dibenzyltrithiodicarbonic acid,
O,O'-dicyclohexyltrithiodicarbonic acid, and
O,O'-dinorbornyltrithiodicarbonic acid. S Valence Stabilizer #12:
Examples of dithiohypophosphoric acids, bis(dithiohypophosphoric
acids), poly(dithiohypophosphoric acids), and derivatives thereof
(S--S Bidentates, S--S Tridentates, S--S Tetradentates) that meet
the requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to: dithiohypophosphoric
acid, methyldithiohypophosphoric acid,
isopropyldithiohypophosphoric acid, tert-butyldithiohypophosphoric
acid, phenyldithiohypophosphoric acid,
pentafluorophenyldithiohypophosphoric acid,
benzyldithiohypophosphoric acid, cyclohexyldithiohypophosphoric
acid, norbornyldithiohypophosphoric acid,
dimethyldithiohypophosphoric acid, diisopropyldiothiohypophosphoric
acid, di-tert-butyldithiohypophosphoric acid,
diphenyldithiohypophosphoric acid,
di-pentafluorophenyldithiohypophosphoric acid,
dibenzyldithiohypophosphoric acid, dicyclohexyldithiohypophosphoric
acid, and dinorbornyldithiohypophosphoric acid. S Valence
Stabilizer #13: Examples of dithiohypophosphoramides,
bis(dithiohypophosphoramides), and poly(dithiohypophosphoramides)
(S--S Bidentates, S--S Tridentates, S--S Tetradentates) that meet
the requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to: dithiohypophosphoramide,
N-methyldithiohypophosphoramide,
N-isopropyldithiohypophosphoramide,
N-tert-butyldithiohypophosphoramide,
N-phenyldithiohypophosphoramide,
N-pentafluorophenyldithiohypophosphoramide,
N-benzyldithiohypophosphoramide,
N-cyclohexyldithiohypophosphoramide,
N-norbornyldithiohypophosphoramide,
N,N'''-dimethyldithiohypophosphoramide,
N,N'''-diisopropyldithiohypophosphoramide,
N,N'''-di-tert-butyldithiohypophosphoramide,
N,N'''-diphenyldithiohypophosphoramide,
N,N'''-di-pentafluorophenyldithiohypophosphoramide,
N,N'''-dibenzyldithiohypophosphoramide,
N,N'''-dicyclohexyldithiohypophosphoramide, and
N,N'''-dinorbornyldithiohypophosphoramide. S Valence Stabilizer
#14: Examples of dithioimidodiphosphoric acids,
dithiohydrazidodiphosphoric acids, bis(dithioimidodiphosphoric
acids), bis(dithiohydrazidodiphosphoric acids),
poly(dithioimidodiphosphoric acids),
poly(dithiohydrazidodiphosphoric acids), and derivatives
thereof(S--S Bidentates, S--S Tridentates, S--S Tetradentates) that
meet the requirements for use as "wide band" valence stabilizers
for Co.sup.+3 include, but are not limited to:
dithioimidodiphosphoric acid, methyldithioimidodiphosphoric acid,
isopropyldithioimidodiphosphoric acid,
tert-butyldithioimidodiphosphoric acid,
phenyldithioimidodiphosphoric acid,
pentafluorophenyldithioimidodiphosphoric acid,
benzyldithioimidodiphosphoric acid,
cyclohexyldithioimidodiphosphoric acid,
norbornyldithioimidodiphosphoric acid,
dimethyldithioimidodiphosphoric acid,
diisopropyldiothioimidodiphosphoric acid,
di-tert-butyldithioimidodiphosphoric acid,
diphenyldithioimidodiphosphoric acid,
di-pentafluorophenyldithioimidodiphosphoric acid,
dibenzyldithioimidodiphosphoric acid,
dicyclohexyldithioimidodiphosphoric acid, and
dinorbornyldithioimidodiphosphoric acid. S Valence Stabilizer #15:
Examples of dithioimidodiphosphoramides,
dithiohydrazidodiphosphoramides, bis(dithioimidodiphosphoramides),
bis(dithiohydrazidodiphosphoramides),
poly(dithioimidodiphosphoramides), and
poly(dithiohydrazidodiphosphoramides) (S--S Bidentates, S--S
Tridentates, S--S Tetradentates) that meet the requirements for use
as "wide band" valence stabilizers for Co.sup.+3 include, but are
not limited to: dithioimidodiphosphoramide,
N-methyldithioimidodiphosphoramide,
N-isopropyldithioimidodiphosphoramide,
N-tert-butyldithioimidodiphosphoramide,
N-phenyldithioimidodiphosphoramide,
N-pentafluorophenyldithioimidodiphosphoramide,
N-benzyldithioimidodiphosphoramide,
N-cyclohexyldithioimidodiphosphoramide,
N-norbornyldithioimidodiphosphoramide,
N,N'''-dimethyldithioimidodiphosphoramide,
N,N'''-diisopropyldithioimidodiphosphoramide,
N,N'''-di-tert-butyldithioimidodiphosphoramide,
N,N'''-diphenyldithioimidodiphosphoramide,
N,N'''-di-pentafluorophenyldithioimidodiphosphoramide,
N,N'''-dibenzyldithioimidodiphosphoramide,
N,N'''-dicyclohexyldithioimidodiphosphoramide, and
N,N'''-dinorbornyldithioimidodiphosphoramide. S Valence Stabilizer
#16: Examples of dithiodiphosphoramides,
bis(dithiodiphosphoramides), and poly(dithiodiphosphoramides) (S--S
Bidentates, S--S Tridentates, S--S Tetradentates) that meet the
requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to: dithiodiphosphoramide,
N-methyldithiodiphosphoramide, N-isopropyldithiodiphosphoramide,
N-tert-butyldithiodiphosphoramide, N-phenyldithiodiphosphoramide,
N-pentafluorophenyldithiodiphosphoramide,
N-benzyldithiodiphosphoramide, N-cyclohexyldithiodiphosphoramide,
N-norbornyldithiodiphosphoramide,
N,N'''-dimethyldithiodiphosphoramide,
N,N'''-diisopropyldithiodiphosphoramide,
N,N'''-di-tert-butyldithiodiphosphoramide,
N,N'''-diphenyldithiodiphosphoramide,
N,N'''-di-pentafluorophenyldithiodiphosphoramide,
N,N'''-dibenzyldithiodiphosphoramide,
N,N'''-dicyclohexyldithiodiphosphoramide, and
N,N'''-dinorbornyldithiodiphosphoramide. S Valence Stabilizer #17:
Examples of dithiodiphosphoric acids, bis(dithiodiphosphoric
acids), poly(dithiodiphosphoric acids), and derivatives thereof
(S--S Bidentates, S--S Tridentates, S--S Tetradentates) that meet
the requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to: dithiodiphosphoric acid,
methyldithiodiphosphoric acid, isopropyldithiodiphosphoric acid,
tert-butyldithiodiphosphoric acid, phenyldithiodiphosphoric acid,
pentafluorophenyldithiodiphosphoric acid, benzylditbiodiphosphoric
acid, cyclohexyldithiodiphosphoric acid,
norbornyldithiodiphosphoric acid, dimethyldithiodiphosphoric acid,
diisopropyldiothiodiphosphoric acid,
di-tert-butyldithiodiphosphoric acid, diphenyldithiodiphosphoric
acid, di-pentafluorophenyldithiodiphosphoric acid,
dibenzyldithiodiphosphoric acid, dicyclohexyldithiodiphosphoric
acid, and dinorbornyldithiodipbosphoric acid. S Valence Stabilizer
#18: Examples of tritbiophosphoric acids (phosphorotrithioic
acids), bis(trithiopbosphoric acids), poly(trithiophosphoric
acids), and derivatives thereof(S--S Bidentates, S--S Tridentates,
S--S Tetradentates) that meet the requirements for use as "wide
band" valence stabilizers for Co.sup.+3 include, but are not
limited to: trithiophosphoric acid, O-phenyltrithiophosphoric acid,
O-benzyltrithiophosphoric acid, O-cyclohexyltrithiophosphoric acid,
O-norbornyltrithiophosphoric acid, O,S-diphenyltrithiophosphoric
acid, O,S-dibenzyltrithiophosphoric acid,
O,S-dicyclohexyltrithiophosphoric acid, and
O,S-dinorbornyltrithiophosphoric acid. S Valence Stabilizer #19:
Examples of dithiophosphoric acids (phosphorodithioic acids),
bis(dithiophosphonic acids), poly(dithiophosphoric acids), and
derivatives thereof(S--S Bidentates, S--S Tridentates, S--S
Tetradentates) that meet the requirements for use as "wide band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
dithiophosphoric acid, O-phenyldithiophosphoric acid,
O-benzyldithiophosphoric acid, O-cyclohexyldithiophosphoric acid,
O-norbornyldithiophosphoric acid, O,O-diphenyldithiophosphoric
acid, O,O-dibenzyldithiophosphoric acid,
O,O-dicyclohexyldithiophosphoric acid, and
O,O-dinorbornyldithiophosphoric acid. S Valence Stabilizer #20:
Examples of tetrathiophosphoric acids (phosphorotetrathioic acids),
bis(tetrathiophosphoric acids), poly(tetrathiophosphoric acids),
and derivatives thereof (S--S Bidentates, S--S Tridentates, S--S
Tetradentates) that meet the requirements for use as "wide band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
tetrathiophosphoric acid, S-phenyltetrathiophosphoric acid,
S-benzyltetrathiophosphoric acid, S-cyclohexyltetrathiophosphoric
acid, S-norbornyltetrathiophosphoric acid,
S,S-diphenyltetrathiophosphoric acid,
S,S-dibenzyltetrathiophosphoric acid,
S,S-dicyclohexyltetrathiophosphoric acid, and
S,S-dinorbornyltetrathiophosphoric acid. S Valence Stabilizer #21:
Examples of phosphoro(dithioperoxo)dithioic acids,
bis[phosphoro(dithioperoxo)dithioic acids],
poly[phosphoro(dithioperoxo)dithioic acids], and derivatives
thereof(S--S Bidentates, S--S Tridentates, S--S Tetradentates) that
meet the requirements for use as "wide band" valence stabilizers
for Co.sup.+3 include, but are not limited to:
phosphoro(dithioperoxo)dithioic acid,
O-phenylphosphoro(dithioperoxo)dithioic acid,
O-benzylphosphoro(dithioperoxo)dithioic acid,
O-cyclohexylphosphoro(dithioperoxo)dithioic acid,
O-norbornylphosphoro(dithioperoxo)dithioic acid,
O,S-diphenylphosphoro(dithioperoxo)dithioic acid,
O,S-dibenzylphosphoro(dithioperoxo)dithioic acid,
O,S-dicyclohexylphosphoro(dithioperoxo)dithioic acid, and
O,S-dinorbornylphosphoro(dithioperoxo)dithioic acid. S Valence
Stabilizer #22: Examples of phosphoro(dithioperoxo)thioic acids,
bis[phosphoro(dithioperoxo)thioic acids],
poly[phosphoro(dithioperoxo)thioic acids], and derivatives thereof
(S--S Bidentates, S--S Tridentates, S--S Tetradentates) that meet
the requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to:
phosphoro(dithioperoxo)thioic acid,
O-phenylphosphoro(dithioperoxo)thioic acid,
O-benzylphosphoro(dithioperoxo)thioic acid,
O-cyclohexylphosphoro(dithioperoxo)thioic acid,
O-norbornylphosphoro(dithioperoxo)thioic acid,
O,S-diphenylphosphoro(dithioperoxo)thioic acid,
O,S-dibenzylphosphoro(dithioperoxo)thioic acid,
O,S-dicyclohexylphosphoro(dithioperoxo)thioic acid, and
O,S-dinorbornylphosphoro(dithioperoxo)thioic acid. S Valence
Stabilizer #23: Examples of phosphoro(dithioperoxo)trithioic acids,
bis[phosphoro(dithioperoxo)trithioic acids],
poly[phosphoro(dithioperoxo)trithioic acids], and derivatives
thereof (S--S Bidentates, S--S Tridentates, S--S Tetradentates)
that meet the requirements for use as "wide band" valence
stabilizers for Co.sup.+3 include, but are not limited to:
phosphoro(dithioperoxo)trithioic acid,
O-phenylphosphoro(dithioperoxo)trithioic acid,
O-benzylphosphoro(dithioperoxo)trithioic acid,
O-cyclohexylphosphoro(dithioperoxo)trithioic acid,
O-norbornylphosphoro(dithioperoxo)trithioic acid,
O,S-diphenylphosphoro(dithioperoxo)trithioic acid,
O,S-dibenzylphosphoro(dithioperoxo)trithioic acid,
O,S-dicyclohexylphosphoro(dithioperoxo)trithioic acid, and
O,S-dinorbornylphosphoro(dithioperoxo)trithioic acid. S Valence
Stabilizer #24: Examples of beta-mercaptothioketones,
beta-mercaptothioaldehydes, bis(beta-mercaptothioketones),
bis(beta-mercaptothioaldehydes), poly(beta-mercaptothioketones),
and poly(beta-mercaptothioaldehydes) (S--S Bidentates, S--S
Tridentates, S--S Tetradentates) that meet the requirements for use
as "wide band" valence stabilizers for Co.sup.+3 include, but are
not limited to: 4-mercaptopentan-2-thione;
1,3-diphenyl-3-mercaptopropanethioaldehyde;
1,3-dibenzyl-3-mercaptopropanethioaldehyde;
1,3-dicyclohexyl-3-mercaptopropanethioaldehyde;
1,3-dinorbornyl-3-mercaptopropanethioaldehyde;
1,3-di(2-thienyl)-3-mercaptopropanethioaldehyde;
1,3-di(2-furyl)-3-mercaptopropanethioaldehyde;
o-mercaptothioacetophenone; 5-mercapto-1,4-dithionaphthoquinone;
1-mercaptothioacridone; 1-mercaptodithioanthraquinone;
1,8-dimercaptodithioanthraquinone; and
beta-mercaptothiobenzophenone. S Valence Stabilizer #25: Examples
of N-(aminomethylthiol)thioureas
[N-(aminomercaptomethyl)thioureas],
bis[N-(aminomethylthiol)thioureas], and
poly[N-(aminomethylthiol)thioureas] (S--S Bidentates, S--S
Tridentates, S--S Tetradentates) that meet the requirements for use
as "wide band" valence stabilizers for Co.sup.+3 include, but are
not limited to: N'-(aminomercaptomethyl)thiourea;
N,N''-dimethyl-N'-(aminomercaptomethyl)thiourea;
N,N'-diethyl-N'-(aminomercaptomethyl)thiourea;
N,N''-isopropyl-N'-(aminomercaptomethyl)thiourea;
N,N''-diphenyl-N'-(aminomercaptomethyl)thiourea;
N,N''-dibenzyl-N'-(aminonercaptomethyl)thiourea;
N,N''-dicyclohexyl-N'-(aminomercaptomethyl)thiourea; and
N,N''-dinorbornyl-N'-(aminomercaptomethyl)thiourea. S Valence
Stabilizer #26: Examples of dithiooxamides, bis(dithiooxamides),
and poly(dithiooxamides) (S--S Bidentates, S--S Tridentates, S--S
Tetradentates) that meet the requirements for use as "wide band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
dithiooxamide (rubeanic acid), N-methyldithiooxamide;
N-ethyldithiooxamide; N-isopropyldithiooxamide;
N-phenyldithiooxamide; N-benzyldithiooxamide;
N-cyclohexyldithiooxamide; N-norbornyldithiooxamide;
N,N'-dimethyldithiooxamide; N,N'-diethyldithiooxamide;
N,N'-diisopropyldithiooxamide; N,N'-diphenyldithiooxamide;
N,N'-dibenzyldithiooxamide; N,N'-dicyclohexyldithiooxamide; and
N,N'-dinorbornyldithiooxamide. S Valence Stabilizer #27: Examples
of 1,1-dithiolates, bis(1,1-dithiolates), and poly(1,1-dithiolates)
(S--S Bidentates and S--S Tetradentates) that meet the requirements
for use as "wide band" valence stabilizers for Co.sup.+3 include,
but are not limited to: 1,1-dicyano-2,2-ethylene dithiolate
(i-mnt); 1,1-dicarboalkoxy-2,2-ethylenedithiolate(DED);
1,1-di(trifluoromethyl)-2,2-ethylenedithiolate;
1,1-di(pentafluorophenyl)-2,2-ethylene dithiolate;
1-pentamethylene-2,2-ethylene dithiolate; and 1-nitroethylene
dithiolate. S Valence Stabilizer #28: Examples of
dithiomonocarboxylic acids, tri- and tetrathiodicarboxylic Acids,
bis(dithiomonocarboxylic acids), bis(tri- and tetrathiodicarboxylic
acids), poly(dithiomonocarboxylic acids), poly(tri- and
tetrathiodicarboxylic acids), and derivatives thereof (S--S
Bidentates and S--S Tetradentates) that meet the
requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to: dithioacetic acid;
dithiopropionic acid; dithiobenzoic acid (dtb); dithiophenylacetic
acid (dtpa); dithiocyclohexanoic acid; dithiofuroic acid;
dithionaphthoic acid; phenyl dithioacetate; phenyl
dithiopropionate; phenyl dithiobenzoate; phenyl
dithiocyclohexanoate; phenyl dithiofuroate; phenyl
dithionaphthoate; tetrathiooxalic acid; tetrathiomalonic acid;
tetrathiosuccinic acid; trithiooxalic acid; trithiomalonic acid;
trithiosuccinic acid; diphenyl tetrathiooxalate; diphenyl
tetrathiomalonate; diphenyl tetrathiosuccinate; diphenyl
trithiooxalate; diphenyl trithiomalonate; diphenyl
trithiosuccinate; pyridine dithiocarboxylic acid; pyrrole
dithiocarboxylic acid; thiophene dithiocarboxylic acid;
dithionaphthoic acid; and tetrathiocamphonic acid. S Valence
Stabilizer #29: Examples of perthiomonocarboxylic acids,
perthiodicarboxylic acids, bis(perthiomonocarboxylic acids),
bis(perthiodicarboxylic acids), poly(perthiomonocarboxylic acids),
poly(perthiodicarboxylic acids), and derivatives thereof (S--S
Bidentates and S--S Tetradentates) that meet the requirements for
use as "wide band" valence stabilizers for Co.sup.+3 include, but
are not limited to: perthioacetic acid; perthiopropionic acid;
perthiobenzoic acid; perthiophenylacetic acid; perthiocyclohexanoic
acid; perthiofuroic acid; perthionaphthoic acid; phenyl
perthioacetate; phenyl perthiopropionate; phenyl perthiobenzoate;
phenyl perthiocyclohexanoate; phenyl perthiofuroate; phenyl
perthionaphthoate; perthiooxalic acid; perthiomalonic acid;
perthiosuccinic acid; diphenyl perthiooxalate; diphenyl
perthiomalonate; diphenyl perthiosuccinate; dithiole-3-thione
(dithione-3-thione); and benzodithiole-3-thione
(benzodithione-3-thione). S Valence Stabilizer #30: Examples of
dithiocarbonates, trithiocarbonates, perthiocarbonates,
bis(dithiocarbonates), bis(trithiocarbonates), and
bis(perthiocarbonates) (S--S Bidentates and S--S Tetradentates)
that meet the requirements for use as "wide band" valence
stabilizers for Co.sup.+3 include, but are not limited to:
S,S-diethyldithiocarbonate; S,S-diisopropyldithiocarbonate;
S,S-diphenyldithiocarbonate; S,S-dibenzyldithiocarbonate;
S,S-dicyclohexyldithiocarbonate; S,S-dinorbornyldithiocarbonate;
diethyltrithiocarbonate; diisopropyltrithiocarbonate;
diphenyltrithiocarbonate; dibenzyltrithiocarbonate;
dicyclohexyltrithiocarbonate; and dinorbornyltrithiocarbonate. S
Valence Stabilizer #31: Examples of dithiocarbamates,
bis(dithiocarbamates), and poly(dithiocarbamates) (including
N-hydroxydithiocarbamates and N-mercaptodithiocarbamates) (S--S
Bidentates, S--S Tridentates, and S--S Tetradentates) that meet the
requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to: dimethyldithiocarbamate
(dmdtc); di(trifluorodimethyl)dithiocarbamate;
diethyldithiocarbamate (dedtc); dipropyldithiocarbamate;
diisopropyldithiocarbamate; dibutyldithiocarbamate;
ditertbutyldithiocarbamate; dicyanamidodithiocarbamate;
azidothioformates; diphenyldithiocarbamate;
di(pentafluorophenyl)dithiocarbamate; dibenzyldithiocarbamate;
dinaphthyldithiocarbamate; dicyclohexyldithiocarbamate;
dinorbornyldithiocarbamate; diadamantyldithiocarbamate;
pyrrolidinodithiocarbamate (pyrdtc); piperidinodithiocarbamate
(pipdtc); morpholinodithiocarbamate (mordtc);
thiamorpholinodithiocarbamate; 3-pyrrolinodithiocarbamate;
pyrrolodithiocarbamate; oxazolodithiocarbamate;
isoxazolodithiocarbamate; thiazolodithiocarbamate;
isothiazolodithiocarbamate; indolodithiocarbamate;
carbazolodithiocarbamate; pyrazolinodithiocarbamate;
imidazolinodithiocarbamate; pyrazolodithiocarbamate;
imidazolodithiocarbamate; indazolodithiocarbamate; and
triazolodithiocarbamate. S Valence Stabilizer #32: Examples of
dithiocarbazates (dithiocarbazides), bis(dithiocarbazates), and
poly(dithiocarbazates) (S--S Bidentates, S--S Tridentates, and S--S
Tetradentates; or possibly N--S Bidentates, N--S Tridentates, and
N--S Tetradentates) that meet the requirements for use as "wide
band" valence stabilizers for Co.sup.+3 include, but are not
limited to: N,N'-dimethyldithiocarbazate;
N,N'-di(trifluoromethyl)dithiocarbazate;
N,N'-diethyldithiocarbazate; N,N'-diphenyldithiocarbazate;
N,N'-dibenzyldithiocarbazate;
N,N'-di(pentafluorophenyl)dithiocarbazate;
N,N'-dicyclohexyldithiocarbazate; and
N,N'-dinorbornyldithiocarbazate. N--S Valence Stabilizer #1:
Examples of diformamidine disulfides (thioperoxydicarbonimidic
diamides), thioperoxytricarbonimidic diamides,
thioperoxytetracarbonimidic diamides, bis(diformamidine
disulfides), and poly(diformamidine disulfides) (N--S bidentates,
N--N--S tridentates, or N--S tetradentates) that meet the
requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to: diformamidine disulfide;
methyldiformamidine disulfide; ethyldiformamidine disulfide;
isopropyldiformamidine disulfide; butyldiformamidine disulfide;
benzyldiformamidine disulfide; phenyldiformamidine disulfide;
tolyldiformamidine disulfide; naphthyldiformamidine disulfide;
cyclohexyldiformamidine disulfide; norbornyldiformamidine
disulfide; adamantyldiformamidine disulfide; dimethyldiformamidine
disulfide; diethyldiformamidine disulfide; diisopropyldiformamidine
disulfide; dibutyldiformamidine disulfide; dibenzyldiformamidine
disulfide; diphenyldiformamidine disulfide; ditolyldiformamidine
disulfide; dinaphthyldiformamidine disulfide;
dicyclohexyldiformamidine disulfide; dinorbornyldiformamidine
disulfide; diadamantyldiformamidine disulfide;
2-S-amidinodisulfidothiazole; 2-S-amidinodisulfidooxazole;
2-S-amidinodisulfidoimidazole; 3-S-amidinodisulfidopyrazole;
3-S-amidinodisulfido-1,2,4-triazole; and
5-S-amidinodisulfidotetrazole. N--S Valence Stabilizer #2: Examples
of S-amidinodithiocarbamates, bis(S-amidinodithiocarbamates), and
poly(S-amidinodithiocarbamates) (N--S Bidentates and N--S
Tetradentates) that meet the requirements for use as "wide band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
S-amidinodithiocarbamate; N-methyl-S-amidinodithiocarbamate;
N-ethyl-S-amidinodithiocarbamate;
N-isopropyl-S-amidinodithiocarbamate;
N-butyl-S-amidinodithiocarbamate;
N-benzyl-S-amidinodithiocarbamate;
N-phenyl-S-amidinodithiocarbamate;
N-tolyl-S-amidinodithiocarbamate;
N-naphthyl-S-amidinodithiocarbamate;
N-cyclohexyl-S-amidinodithiocarbamate;
N-norbornyl-S-amidinodithiocarbamate;
N-adamantyl-S-amidinodithiocarbamate;
N,N'-dimethyl-S-amidinodithiocarbamate;
N,N'-diethyl-S-amidinodithiocarbamate;
N,N'-diisopropyl-S-amidinodithiocarbamate;
N,N'-dibutyl-S-amidinodithiocarbamate;
N,N'-dibenzyl-S-amidinodithiocarbamate;
N,N'-diphenyl-S-amidinodithiocarbamate;
N,N'-ditolyl-S-amidinodithiocarbamate;
N,N'-dinaphthyl-S-amidinodithiocarbamate;
N,N'-dicyclohexyl-S-amidinodithiocarbamate;
N,N'-dinorbornyl-S-amidinodithiocarbamate;
N,N'-diadamantyl-S-amidinodithiocarbamate;
ethylenebis(S-amidinodithiocarbamate);
propylenebis(S-amidinodithiocarbamate);
phenylenebis(S-amidinodithiocarbamate);
piperazinebis(S-amidinodithiocarbamate);
oxalylbis(S-amidinodithiocarbamate);
malonylbis(S-amidinodithiocarbamate);
succinylbis(S-amidinodithiocarbamate);
phthalylbis(S-amidinodithiocarbamate); 2-S-dithiocarbamatothiazole;
2-S-dithiocarbamatooxazole; 2-S-dithiocarbamatoimidazole;
3-S-dithiocarbamatopyrazole; 3-S-dithiocarbamato-1,2,4-triazole;
and 5-S-dithiocarbamatotetrazole. N--S Valence Stabilizer #3:
Examples of O-amidinothiocarbamates, bis(O-amidinothiocarbamates),
and poly(O-amidinothiocarbamates) (N--S Bidentates and N--S
Tetradentates) that meet the requirements for use as "wide band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
O-amidinothiocarbamate; N-methyl-O-amidinothiocarbamate;
N-ethyl-O-amidinothiocarbamate; N-isopropyl-O-amidinothiocarbamate;
N-butyl-O-amidinothiocarbamate; N-benzyl-O-amidinothiocarbamate;
N-phenyl-O-amidinothiocarbamate; N-tolyl-O-amidinothiocarbamate;
N-naphthyl-O-amidinothiocarbamate;
N-cyclohexyl-O-amidinothiocarbamate;
N-norbornyl-O-amidinothiocarbamate;
N-adamantyl-O-amidinothiocarbamate;
N,N'-dimethyl-O-amidinothiocarbamate;
N,N'-diethyl-O-amidinothiocarbamate;
N,N'-diisopropyl-O-amidinothiocarbamate;
N,N'-dibutyl-O-amidinothiocarbamate;
N,N'-dibenzyl-O-amidinothiocarbamate;
N,N'-diphenyl-O-amidinothiocarbamate;
N,N'-ditolyl-O-amidinothiocarbamate;
N,N'-dinaphthyl-O-amidinothiocarbamate;
N,N'-dicyclohexyl-O-amidinothiocarbamate;
N,N'-dinorbornyl-O-amidinothiocarbamate;
N,N'-diadamantyl-O-amidinothiocarbamate;
ethylenebis(O-amidinothiocarbamate);
propylenebis(O-amidinothiocarbamate);
phenylenebis(O-amidinothiocarbamate);
piperazinebis(O-amidinothiocarbamate);
oxalylbis(O-amidinothiocarbamate);
malonylbis(O-amidinothiocarbamate);
succinylbis(O-amidinothiocarbamate);
phthalylbis(O-amidinothiocarbamate); 2-O-monothiocarbamatothiazole;
2-O-monothiocarbamatooxazole; 2-O-monothiocarbamatoimidazole;
3-O-monothiocarbamatopyrazole;
3-O-monothiocarbamato-1,2,4-triazole; and
5-O-monothiocarbamatotetrazole. N--S Valence Stabilizer #4:
Examples of S-amidinoperoxythiocarbamates,
bis(S-amidinoperoxythiocarbamates), and
poly(S-amidinoperoxythiocarbamates) (N--S Bidentates and N--S
Tetradentates) that meet the requirements for use as "wide band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
S-amidinoperoxythiocarbamate;
N-methyl-S-amidinoperoxythiocarbamate;
N-ethyl-S-amidinoperoxythiocarbamate;
N-isopropyl-S-amidinoperoxythiocarbamate;
N-butyl-S-amidinoperoxythiocarbamate;
N-benzyl-S-amidinoperoxythiocarbamate;
N-phenyl-S-amidinoperoxythiocarbamate;
N-tolyl-S-amidinoperoxythiocarbamate;
N-naphthyl-S-amidinoperoxythiocarbamate;
N-cyclohexyl-S-amidinoperoxythiocarbamate;
N-norbornyl-S-amidinoperoxythiocarbamate;
N-adamantyl-S-amidinoperoxythiocarbamate;
N,N'-dimethyl-S-amidinoperoxythiocarbamate;
N,N'-diethyl-S-amidinoperoxythiocarbamate;
N,N'-diisopropyl-S-amidinoperoxythiocarbamate;
N,N'-dibutyl-S-amidinoperoxythiocarbamate;
N,N'-dibenzyl-S-amidinoperoxythiocarbamate;
N,N'-diphenyl-S-amidinoperoxythiocarbamate;
N,N'-ditolyl-S-amidinoperoxythiocarbamate;
N,N'-dinaphthyl-S-amidinoperoxythiocarbamate;
N,N'-dicyclohexyl-S-amidinoperoxythiocarbamate;
N,N'-dinorbornyl-S-amidinoperoxythiocarbamate;
N,N'-diadamantyl-S-amidinoperoxythiocarbamate;
ethylenebis(S-amidinoperoxythiocarbamate);
propylenebis(S-amidinoperoxythiocarbamate);
phenylenebis(S-amidinoperoxythiocarbamate);
piperazinebis(S-amidinoperoxythiocarbamate);
oxalylbis(S-amidinoperoxythiocarbamate);
malonylbis(S-amidinoperoxythiocarbamate);
succinylbis(S-amidinoperoxythiocarbamate); and
phthalylbis(S-amidinoperoxythiocarbamate). N--S Valence Stabilizer
#5: Examples of phosphorimidothioic acid; phosphorimidodithioic
acid; phosphorimidotrithioic acid; bis(phosphorimidothioic acid);
bis(phosphorimidodithioic acid); bis(phosphorimidotrithioic acid);
poly(phosphorimidothioic acid); poly(phosphorimidodithioic acid);
poly(phosphorimidotrithioic acid); and derivatives thereof (N--S
Bidentates and N--S Tetradentates) that meet the requirements for
use as "wide band" valence stabilizers for Co.sup.+3 include, but
are not limited to: phosphorimidothioic acid; phosphorimidodithioic
acid; phosphorimidotrithioic acid; O-phenylphosphorimidothioic
acid; O-benzylphosphorimidothioic acid;
O-cyclohexylphosphorimidothioic acid;
O-norbornylphosphorimidothioic acid;
O,O'-diphenylphosphorimidothioic acid;
O,O'-dibenzylphosphorimidothioic acid;
O,O'-dicyclohexylphosphorimidothioic acid; and
O,O'-dinorbornylphosphorimidothioic acid. N--S Valence Stabilizer
#6: Examples of phosphorothioic triamides, bis(phosphorothioic
triamides), and poly(phosphorothioic triamides) (N--S Bidentates
and N--S Tetradentates) that meet the requirements for use as "wide
band" valence stabilizers for Co.sup.+3 include, but are not
limited to: phosphorothioic triamide; phosphorothioic trihydrazide;
phosphoramidothioic dihydrazide; N-phenylphosphorothioic
triamide;N-benzylphosphorothioic triamide;
N-cyclohexylphosphorothioic triamide; N-norbornylphosphorothioic
triamide; N,N'-diphenylphosphorothioic triamide;
N,N'-dibenzylphosphorothioic triamide;
N,N'-dicyclohexylphosphorothioic triamide; and
N,N'-dinorbornylphosphorothioic triamide. N--S Valence Stabilizer
#7: Examples of phosphoramidotrithioic acid,
phosphorodiamidodithioic acid, bis(phosphoramidotrithioic acid),
bis(phosphorodiamidodithioic acid), poly(phosphoramidotrithioic
acid), poly(phosphorodiamidodithioic acid), and derivatives thereof
(N--S Bidentates and N--S Tetradentates) that meet the requirements
for use as "wide band" valence stabilizers for Co.sup.+3 include,
but are not limited to: phosphoramidotrithioic acid,
phosphorodiamidodithioic acid, S-phenylphosphoramidotrithioic acid,
S-benzylphosphoramidotrithioic acid,
S-cyclohexylphosphoramidotrithioic acid,
S-norbornylphosphoramidotrithioic acid,
S,S'-diphenylphosphoramidotrithioic acid,
S,S'-dibenzylphosphoramidotrithioic acid,
S,S'-dicyclohexylphosphoramidotrithioic acid, and
S,S'-dinorbornylphosphoramidotrithioic acid. N--S Valence
Stabilizer #8: Examples of phosphoramidothioic acid,
phosphoramidodithioic acid, phosphorodiamidothioic acid,
bis(phosphoramidothioic acid), bis(phosphoramidodithioic acid),
bis(phosphorodiamidothioic acid), poly(phosphoramidothioic acid),
poly(phosphoramidodithioic acid), and poly(phosphorodiamidothioic
acid) (N--S Bidentates and N--S Tetradentates) that meet the
requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to: phosphoramidothioic
acid, phosphoramidodithioic acid, phosphorodiamidothioic acid,
phosphorohydrazidothioic acid, phosphorohydrazidodithioic acid,
phosphorodihydrazidothioic acid, phosphoramidohydrazidothioic acid,
O-phenylphosphoramidothioic acid, O-benzylphosphoramidothioic acid,
O-cyclohexylphosphoramidothioic acid,
O-norbornylphosphoramidothioic acid, S-phenylphosphoramidodithioic
acid, S-benzylphosphoramidodithioic acid,
S-cyclohexylphosphoramidodithioic acid, and
S-norbornylphosphoramidodithioic acid. N--S Valence Stabilizer #9:
Examples of N-thioacyl 7-aminobenzylidenimines (N--S Bidentates or
N--S Tetradentates) that meet the requirements for use as "wide
band" valence stabilizers for Co.sup.+3 include, but are not
limited to: N-thioacetyl 7-methylaminobenzylidenimine; N-thioacetyl
7-phenylaminobenzylidenimine; N-thiobenzoyl
7-methylaminobenzylidenimine; and N-thiobenzoyl
7-phenylaminobenzylidenimine. N--S Valence Stabilizer #10: Examples
of thiohydroxamates (thiohydroxylamines), bis(thiohydroxamates),
and poly(thiohydroxamates) (N--S Bidentates, N--S Tetradentates,
and N--S Hexadentates) that meet the requirements for use as "wide
band" valence stabilizers for Co.sup.+3 include, but are not
limited to: acetothiohydroxamic acid; propianothiohydroxamic acid;
butyrothiohydroxamic acid; crotonothiohydroxamic acid;
sorbothiohydroxamic acid; benzothiohydroxamic acid;
toluicthiohydroxamic acid; salicylthiohydroxamic acid;
phenylacetothiohydroxamic acid; anthranilthiohydroxamic acid;
nicotinethiohydroxamic acid; picolinethiohydroxamic acid;
cyclohexanethiohydroxamic acid; quinoline 8-thiohydroxamic acid;
cinnamylthiohydroxamic acid; oxaldithiohydroxamic acid;
succinylbis-N-phenylthiohydroxamic acid;
adipylbis-N-phenylthiohydroxamic acid; glyoxalthiohydroxamic acid;
2-thiophenethiocarbohydroxamic acid; thenoylthiohydroxamic acid;
N-phenylbenzothiohydroxamic acid; N-tolylbenzothiohydroxamic acid;
N-phenylacetothiohydroxamic acid; N-phenyl-2-thenoylthiohydroxainic
acid; and N-tolyl-2-thenoylthiohydroxamic acid. N--S Valence
Stabilizer #11: Examples of alpha- or ortho-aminothiocarboxylic
acids, and alpha- or ortho-aminothiodicarboxylic acids, and
derivatives thereof (N--S Bidentates, N--S Tridentates, and N--S
Tetradentates) that meet the requirements for use as "wide band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
2-pyridinethiocarboxylic acid (thiopicolinic acid);
2-pyrazinethiocarboxylic acid; o-aminothiobenzoic acid;
o-aminothionaphthoic acid; and 3,6-diaminothiophthalic acid. N--S
Valence Stabilizer #12: Examples of thiosemicarbazones,
bis(thiosemicarbazones), and poly(thiosemicarbazones) (N--S
Bidentates, N--S Tetradentates, and N--S Hexadentates) that meet
the requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to: acetaldehyde
thiosemicarbazone; acetone thiosemicarbazone; pinacolone
thiosemicarbazone; benzaldehyde thiosemicarbazone; naphthaldehyde
thiosemicarbazone; norbornanone thiosemicarbazone; camphor
thiosemicarbazone; nopinone thiosemicarbazone; 2-pyridinaldehyde
thiosemicarbazone; salicylaldehyde thiosemicarbazone;
quinolinaldehyde thiosemicarbazone; isatin dithiosemicarbazone;
camphorquinone dithiosemicarbazone; camphorquinone
dithiosemicarbazone; picolinaldehyde thiosemicarbazone; dipyridyl
glyoxal dithiosemicarbazone; di-2-pyridyl ketone thiosemicarbazone;
methyl-2-pyridyl ketone thiosemicarbazone; glyoxal
dithiosemicarbazone; acetophenone thiosemicarbazone; biacetyl
monoxime thiosemicarbazone; acetamidobenzaldehyde
thiosemicarbazone; thymolaldothiosemicarbazone;
thiophene-2-aldehyde thiosemicarbazone; phthalaldehyde
dithiosemicarbazone; phthalimide dithiosemicarbazone; furaldehyde
thiosemicarbazone; naphthoquinone thiosemicarbazone;
phenanthrequinone thiosemicarbazone; cyclohexanedione
dithiosemicarbazone; ionone thiosemicarbazone; bisthiosemicarbazone
of diethyl-3,4-dioxadioate; pyridoxal alkylthiosemicarbazones;
benzylidene phenylthiosemicarbazones; lawsone thiosemicarbazone;
and 1-benzoin-4-phenylthiosemicarbazone (bps). N--S Valence
Stabilizer #13: Examples of thioacyl hydrazones, bis(thioacyl
hydrazones), and poly(thioacyl hydrazones) (N--S Bidentates, N--S
Tetradentates, and N--S Hexadentates) that meet the requirements
for use as "wide band" valence stabilizers for Co.sup.+3 include,
but are not limited to: acetaldehyde N-thioformylhydrazone;
acetaldehyde N-thiobenzoylhydrazone; acetone N-thioformylhydrazone;
acetone N-thiobenzoylhydrazone; pinacolone N-thioformylhydrazone;
pinacolone N-thiobenzoylhydrazone; benzaldehyde
N-thioformylhydrazone; benzaldehyde N-thiobenzoylhydrazone;
naphthaldehyde N-thioformylhydrazone; naphthaldehyde
N-thiobenzoylhydrazone; norbornanone N-thioformylhydrazone;
norbornanone N-thiobenzoylhydrazone; camphor N-thioformylhydrazone;
camphor N-thiobenzoylhydrazone; nopinone N-thioformylhydrazone;
nopinone N-thiobenzoylhydrazone; 2-pyridinaldehyde
N-thioformylhydrazone; 2-pyridinaldehyde N-thiobenzoylhydrazone;
salicylaldehyde N-thioformylhydrazone; salicylaldehyde
N-thiobenzoylhydrazone; quinolinaldehyde N-thioformylhydrazone;
quinolinaldehyde N-thiobenzoylhydrazone; thiophene-2-aldehyde
N-thioformylhydrazone; thiophene-2-aldehyde N-thiobenzoylhydrazone;
naphthoquinone N-thioformylhydrazone; naphthoquinone
N-thiobenzoylhydrazone; ionone N-thioformylhydrazone; ionone
N-thiobenzoylhydrazone; benzaldehyde benzothiazolehydrazone;
lawsone N-thioformylhydrazone; and lawsone N-thiobenzoylhydrazone.
N--S Valence Stabilizer #14: Examples of thiocarbazones
(diazenecarbothioic hydrazides), bis(thiocarbazones), and
poly(thiocarbazones) (N--S Bidentates, N--S Tetradentates, and N--S
Hexadentates) that meet the requirements for use as "wide band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
diphenylthiocarbazone (dithizone); 2-phenylthiocarbazone;
dinaphthylthiocarbazone; 2-naphthylthiocarbazone; and ambazone.
N--S Valence Stabilizer #15: Examples of azo compounds with thiol
or mercapto or thiocarbonyl substitution at the ortho- (for aryl)
or alpha- or beta- (for alkyl) positions, Bis[o-(HS--) or alpha- or
beta-(HS--)azo compounds], or Poly[o-(HS--) or alpha- or
beta-(HS--)azo compounds) (N--S Bidentates, N--S Tridentates, N--S
Tetradentates, or N--S Hexadentates) that meet the requirements for
use as "wide band" valence stabilizers for Co.sup.+3 include, but
are not limited to: 2-thiolazobenzene [1-(phenylazo)-2-thiophenol];
2,2'-dithioazobenzene; (2-thiophene)azobenzene;
1-(4-nitrophenylazo)-2-thionaphthol; 2-thiazolylazobenzene; and
2-benzothiazolylazobenzene. N--S Valence Stabilizer #16: Examples
of diazeneformothioamides, diazeneacetothioamides,
bis(diazeneformothioamides), bis(diazeneacetothioamides),
poly(diazeneformothioamides), and poly(diazeneacetothioamides)
(N--S Bidentates, N--S Tetradentates, and N--S Hexadentates) that
meet the requirements for use as "wide band" valence stabilizers
for Co.sup.+3 include, but are not limited to:
diazeneformothioamide, diazeneacetothioamide,
phenyldiazeneformothioamide, diphenyldiazeneformothioamide,
phenyldiazeneacetothioamide, and diphenyldiazeneacetothioamide.
N--S Valence Stabilizer #17: Examples of diazenecarbothioic acids,
diazenecarbodithioic acids, bis(diazenecarbothioic acids),
bis(diazenecarbodithioic acids), poly(diazenecarbothioic acids),
poly(diazenecarbodithioic acids) and derivatives thereof (N--S
Bidentates, N--S Tetradentates, N--S Hexadentates) that meet the
requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to: diazeneformothioic acid,
diazeneacetothioic acid, phenyldiazeneformothioic acid,
diphenyldiazeneformothioic acid, phenyldiazeneacetothioic acid, and
diphenyldiazeneacetothioic acid. N--S Valence Stabilizer #18:
Examples of diazeneformothioaldehydes, diazeneacetothioaldehydes,
bis(diazeneformothioaldehydes), bis(diazeneacetothioaldehydes),
poly(diazeneformothioaldehydes), and
poly(diazeneacetothioaldehydes) (N--S Bidentates, N--S
Tetradentates and N--S Hexadentates) that meet the requirements for
use as "wide band" valence stabilizers for Co.sup.+3 include, but
are not limited to: diazeneformotbioaldehyde,
diazeneacetothioaldehyde, phenyldiazeneformothioaldehyde,
diphenyldiazeneformothioaldehyde, phenyldiazeneacetothioaldehyde,
and diphenyldiazeneacetothioaldehyde. N--S Valence Stabilizer #19:
Examples of diazenediformothioamides, diazenediacetothioamides,
bis(diazenediformothioamides), bis(diazenediacetothioamides),
poly(diazenediformothioamides), and poly(diazenediacetothioamides)
(N--S Tridentates and N--S Hexadentates) that meet the requirements
for use as "wide band" valence stabilizers for Co.sup.+3 include,
but are not limited to: diazenediformodithioamide,
diazenediacetodithioamide, diphenydiazenediformodithioamide,
tetraphenyldiazenediformodithioamide,
diphenyldiazenediacetodithioamide, and
tetraphenyldiazenediacetodithioamide. N--S Valence Stabilizer #20:
Examples ofdiazenedicarbothioic acids, diazenedicarbodithioic
acids, bis(diazenedicarbothioic acids), bis(diazenedicarbodithioic
acids), poly(diazenedicarbothioic acids),
poly(diazenedicarbodithioic acids) and derivatives thereof (N--S
Tridentates and N--S Hexadentates) that meet the requirements for
use as "wide band" valence stabilizers for Co.sup.+3 include, but
are not limited to: diazenediformothioic acid,
diazenediacetodithioic acid, phenyldiazenediformothioic acid,
diphenyldiazenediformothioic acid, phenyldiazenediacetodithioic
acid, and diphenyldiazenediacetodithioic acid. N--S Valence
Stabilizer #21: Examples of diazenediformothioaldehydes,
diazenediacetothioaldehydes, bis(diazenediformothioaldehydes),
bis(diazenediacetothioaldehydes),
poly(diazenediformothioaldehydes), and
poly(diazenediacetothioaldehydes) (N--S Tridentates and N--S
Hexadentates) that meet the requirements for use as "wide band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
diazenediformothioaldehyde, diazenediacetothioaldehyde,
diphenyldiazenediformothioaldehyde, and
diphenyldiazenediacetothioaldehyde. N--S Valence Stabilizer #22:
Examples of ortho-thio (or -mercapto) substituted formazans,
bis(o-thio or -mercapto substituted formazans), and poly(o-thio or
-mercapto substituted formazans) (N--S Bidentates, N--S
Tridentates, N--S Tetradentates, and N--S Hexadentates) that meet
the requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to:
1-(2-thiophenyl)-3,5-diphenylformazan;
1-(2-methylmercaptophenyl)-3,5-diphenylformazan;
1,5-bis(2-thiophenyl)-3-phenylform azan; and
5-bis(2-methylmercaptophenyl)-3-phenylformazan. N--S Valence
Stabilizer #23: Examples of ortho-thio (or -mercapto) substituted
azines (including ketazines), bis(o-thio or mercapto substituted
azines), and poly(o-thio or mercapto substituted azines) (N--S
Bidentates, N--S Tridentates, N--S Tetradentates, and N--S
Hexadentates) that meet the requirements for use as "wide band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
2-mercapto-1-benzalazine; 2-mercapto-1-naphthalazine; and
2-mercapto-1-cyclohexanonazine. N--S Valence Stabilizer #24:
Examples of Schiff Bases with one Imine (C.dbd.N) Group and with
ortho- or alpha- or beta-thio or mercapto or thiocarbonyl
substitution (N--S Bidentates, N--S Tridentates, N--S
Tetradentates, N--S Pentadentates, or N--S Hexadentates) that meet
the requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to: N
-(Thiosalicylaldehydo)isopropylamine;
N-(2-thiophenecarboxaldehydo)isopropylamine;
N-(2-Acetylthiopheno)isopropylamine;
N-(2-Thioacetophenono)isopropylamine;
N-(Thiosalicylaldehydo)cyclohexylamine;
N-(2-Thiophenecarboxaldehydo)cyclohexylamine;
N-(2-Acetylthiopheno)cyclohexylamine;
N-(2-Thioacetophenono)cyclohexylamine;
N-(Thiosalicylaldehydo)aniline;
N-(2-Thiophenecarboxaldehydo)aniline; N-(2-Acetylthiopheno)aniline;
N-(2-Thioacetophenono)aniline;
N-(Thiosalicylaldehydo)aminonorbornane;
N-(2-Thiocarboxaldehydo)aminonorbornane;
N-(2-Acetylthiopheno)aminonorbornane;
N-(2-Thioacetophenono)aminonorbornane;
4-aminobenzylidene-3-propyl-5-mercapto-1,2,4-triazole;
4-aminocinnamalidene-3-propyl-5-mercapto-1,2,4-triazole (acpmt);
4-aminosalicylidene-3-propyl-5-mercapto-1,2,4-triazole (aspmt);
4-aminovanillidene-3-propyl-5-mercapto-1,2,4-triazole;
4-aminodimethylaminobenzylidene-3-propyl-5-mercapto-1,2,4-triazole
(adpmt); cinnamylideneaminophenylthiazole;
N-(2-mercaptophenyl)salicylidenimine; 2-thiophenecarboxaldehyde
phenylhydrazone; 2-thiophenecarboxaldehyde 2-pyridyl hydrazone;
2-mercaptobenzaldehyde phenylhydrazone; and 2-mercaptobenzaldehyde
2-pyridyl hydrazone. Also includes SchiffBases derived from the
reaction of carbonyl compounds with dithiocarbazates, and
hydrazones with ortho-S substitution. N--S Valence Stabilizer #25:
Examples of Schiff Bases with two Imine (C.dbd.N) Groups and with
ortho- or alpha- or beta-thio or mercapto or thiocarbonyl
substitution (N--S Tridentates, N--S Tetradentates, N--S
Pentadentates, or N--S Hexadentates) that meet the requirements for
use as "wide band" valence stabilizers for Co.sup.+3 include, but
are not limited to: N,N'-(2,5-Thiophenedicarboxalehydo)
diisopropylamine;
N,N'-(2,5-Thiophenedicarboxaldehydo)dicyclohexylamine;
N,N'-(2,5-Thiophenedicarboxaldehydo)dianiline;
N,N'-(2,5-Thiophenedicarboxaldehydo)di-aminonorbornane;
N,N'-(o-Thiophthalicdialdehydo)diisopropylamine;
N,N'-(o-Thiophthalicdialdehydo)dicyclohexylamine;
N,N'-(o-Thiophthalicdialdehydo)dianiline;
N,N'-(o-Thiophthalicdialdehydo)di-aminonorbornane;
N,N'-(o-Thioformylcamphoro)diisopropylamine;
N,N'-(o-Thioformylcamphoro)dicyclohexylamine;
N,N'-(o-Thioformylcamphoro)dianiline;
N,N'-(o-Thioformylcamphoro)di-aminonorbornane;
N,N'-(o-Thiodiacetylbenzeno)diisopropylamine;
N,N'-(o-Thiodiacetylbenzeno)dicyclohexylamine;
N,N'-(o-Thiodiacetylbenzeno)dianiline;
N,N'-(o-Thiodiacetylbenzeno)di-aminonorbornane;
N,N'-(3,6-Dithio-1,2-cyclohexanono)diisopropylamine;
N,N'-(3,6-Dithio-1,2-cyclohexanono)dicyclohexylamine;
N,N'-(3,6-Dithio-1,2-cyclohexanono)dianiline;
N,N'-(3,6-Dithio-1,2-cyclohexanono)di-aminonorbornane;
N,N'-(2,5-Diacetylthiopheno)diisopropylamine;
N,N'-(2,5-Diacetylthiopheno)dicyclohexylamine;
N,N'-(2,5-Diacetylthiopheno)dianiline;
N,N'-(2,5-Diacetylthiopheno)di-aminonorbornane;
N,N'-(Thiosalicylaldehydo)ethylenediamine;N,N'-(o-Thionaphthaldehydo)ethy-
lenediamine; N,N'-(o-Thioacetophenono)ethylenediamine;
N,N'-(Thiosalicylaldehydo)trimethylenediamine;
N,N'-(o-Thionaphthaldehydo)trimethylenediamine;
N,N'-(o-Thioacetophenono)trimethylenediamine;
N,N'-(Thiosalicylaldehydo)cyclohexane-1,2-diamine;
N,N'-(o-Thionaphthaldehydo)cyclohexane-1,2-diamine;
N,N'-(o-Thioacetophenono)cyclohexane-1,2-diamine;
N,N'-(Thiosalicylaldehydo)-1,2-diaminobenzene;
N,N'-(o-Thionaphthaldehydo)-1,2-diaminobenzene; and
N,N'-(o-Thioacetophenono)-1,2-diaminobenzene. Also includes
SchiffBases derived from the reaction of carbonyl compounds with
dithiocarbazates, and hydrazones with ortho-S substitution. N--S
Valence Stabilizer #26: Examples of Schiff Bases with three Imine
(C.dbd.N) Groups and with ortho- or alpha- or beta-thio or mercapto
or thiocarbonyl substitution (N--S Tetradentates, N--S
Pentadentates, or N--S Hexadentates) that meet the requirements for
use as "wide band" valence stabilizers for Co.sup.+3 include, but
are not limited to:
N,N',N''-(Thiosalicylaldehydo)tris(2-aminoethyl)amine;
N,N',N''-(o-Thionaphthaldehydo)tris(2-aminoethyl)amine; and
N,N',N''-(o-Thioacetophenono)tris(2-aminoethyl)amine. Also includes
Schiff Bases derived from the reaction of carbonyl compounds with
dithiocarbazates, and hydrazones with ortho-S substitution. N--S
Valence Stabilizer #27: Examples of thioalkyl amines (aminothiols
or aminodisulfides) and thioalkyl imines (iminothiols or
iminodisulfides) (N--S Bidentates, N--S Tridentates, N--S
Tetradentates, and N--S Hexadentates) that meet the requirements
for use as "wide band" valence stabilizers for Co.sup.+3 include,
but are not limited to: 2-mercapto-1-aminoethane;
2-methylmercapto-1-aminoethane; 3-mercapto-1-aminopropane;
1-mercapto-2-amino-2-methylpropane; 2-mercaptocyclohexylamine;
3-mercapto-2-aminonorbornane; 1,3-dimercapto-2-aminopropane;
1,5-dimercapto-3-aminopentane; 2,2'-diaminodiethyl sulfide;
3,3'-diaminodipropyl sulfide; 2,2'-diaminodicyclohexyl sulfide;
1,6-dimercapto-3,4-diaminohexane;
1,7-dimercapto-3,5-diaminoheptane;
1,6-diamino-3,4-dimercaptohexane;
1,7-diamino-3,5-dimercaptoheptane; tri(mercaptomethyl)amine;
tri(2-mercaptoethyl)amine; dithiooxamide (rubeanic acid);
2,2'-diaminodiethyl disulfide; 3,3'-diaminodipropyl disulfide;
2,2'-diaminodicyclohexyl disulfide;
3-amino-1,5-pentanedithiodialdehyde;
3,4-diamino-1,6-hexanedithiodialdehyde;
3,5-diamino-1,7-heptanedithiodialdehyde; iminobisacetic acid;
iminobispropionic acid; and bis(hydroxyethyl)aminoalkyl sulfide.
N--S Valence Stabilizer #28: Examples of thioaryl amines and
thioaryl imines (N--S Bidentates, N--S Tridentates, N--S
Tetradentates, and N--S
Hexadentates) that meet the requirements for use as "wide band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
2-aminothiophenol (2-aminobenzenethiol); 2-aminothiobenzoic acid
(thioanthranilic acid); 2-aminothioanisole; 2-(methanamine)benzyl
mercaptan [(2-aminomethyl)-alpha-toluenethiol]
[(2-mercaptomethyl)-alpha-aminotoluene];
1-amino-2-naphthalenethiol; 2-amino-1-naphthalenethiol;
2-amino-1-(methyldisulfido)benzene;
2,2'-di(aminomethyl)diphenylthioketone; di(2-amino)phenyl sulfide;
di(2-amino)phenyl disulfide (di-ortho-aminophenyl disulfide
(doapd); 1,3-di(2-amino)phenyl-2-mercaptopropane;
1,3-di(3-amino)phenyl-2-mercaptopropane;
1,3-di(2-mercapto)phenyl-2-aminopropane;
1,3-di(3-mercapto)phenyl-2-aminopropane;
2,2'-dimercaptoiminodibenzyl; 2,2'-iminodibenzothioic acid;
2,2'-dimercaptoiminostilbene; and poly(o-aminothiophenol). N--S
Valence Stabilizer #29: Examples of five-membered heterocyclic
rings containing one, two, three, or four nitrogen atoms at least
one additional sulfur atom binding site not in a ring (N--S
Bidentates, N--S Tridentates, N--S Tetradentates, or N--S
Hexadentates) that meet the requirements for use as "wide band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
2-mercaptopyrrole; 2-(methylthio)methylpyrrole;
2,5-(thiomethyl)pyrrole; 2,5-(methylthiomethyl)pyrrole;
2,6-(methyldisulfidomethyl)pyrrole; imidazoline-2-thione
(2-mercaptoimidazole); 2-mercaptothiazoline;
2-mercaptobenzimidazole; 2-mercaptobenzothiazole;
2-mercaptobenzoxazole; 2-thiohydantoin; di-2-pyridylthioglyoxal
(2,2'-thiopyridil); bis((1-pyrazolyl)methane)sulfide;
bis((1-pyrazolyl)methane)disulfide;
bis(2-(1-pyrazolyl)ethane)sulfide;
bis(2-(1-pyrazolyl)ethane)disulfide;
bis(benzimidazolylmethane)sulfide;
bis(benzimidazolylethane)sulfide;
bis(benzimidazolylmethane)disulfide;
bis(benzimidazolylethane)disulfide; tris(imidazolyl)methanethiol;
tris(imidazolylmethane)methanethiol;
N-thiomethyl-N,N-(benzimidazolylmethane)amine;
N-(2-thioethyl)-N,N-(benzimidazolylmethane)amine;
N,N'-di(benzimidazolylmethane)-1,3-diamino-2-mercaptopropane;
N,N,N',N'-tetrakis(benzimidazolylmethane)-1,3-diamino-2-mercaptopropane;
bis(N,N-((4-imidazolyl)methane)2-aminoethane)sulfide;
bis(N,N-((4-imidazolyl)methane)2-aminoethane)disulfide;
2-aminobenzothiazole (abt); 2-phenylaminothiazole; thiohydantoin;
thioxohydropyrazole; 2-mercaptobenzothiazole (mbt);
2-mercapto-1,3,4-thiadiazole; 2,5-dimercapto-1,3,4-thiadiazole
(bismuthiol); 2,5-bis(alkylthio)-1,3,4-thiadiazole;
2-amino-5-mercapto-1,3,4-thiadiazole (amt); 5-mercaptotetrazole;
1-phenyl-5-mercaptotetrazole (pmt)(5-mptt); 5-mercaptotriazole;
3-mercaptotriazole; (2-benzothiazolyl)thioacetic acid;
(2-benzothiazolyl)thiopropionic acid; (alkylthio)benzotriazoles;
(arylthio)benzotriazoles; 2-mercaptopyrimidine;
bis(5-mercapto-1,2,4-triazol-3-yl);
bis(5-mercapto-1,2,4-triazol-3-yl)alkanes; 2-aminothiazolidine;
thiazolidine-2-thione; 2-mercaptothiazolidine;
1-(2-mercaptoethyl)imidazoline; imidazolidine-2-thione;
4,5-dihydroxyimidazolidine-2-thione;
4-amino-5-mercapto-1,2,4-triazole; (2-benzimidazolylthio)carboxylic
acids; (2-benzoxazolylthio)carboxylic acids;
(2-benzothiazolylthio)carboxylic acids;
(2-benzimidazolylthio)hydroxyalkyl(aryl)s;
(2-benzoxazolylthio)hydroxyalkyl(aryl)s;
(2-benzothiazolylthio)hydroxyalkyl(aryl)s;
2-(phenylmethylthio)benzothiazole;
2,5-bis(hydrocarbyldithio)-1,3,4-thiadiazoles;
2-(hydrocarbyldithio)-5-mercapto-1,3,4-thiadiazoles;
bis(dithiobisthiadiazole); benzothiazolethione;
3-hydrazino-5-thio-1,2,4-triazole; imidazolidine-2,4-dithione;
dimercaptobenzothiazole; 2-aminothiazole (atz);
thiadiazole-2-thione; 5-mercaptothiadiazole-2-thione;
1,1-thiocarbonyldiimidazole;
phosphosphonomethylenethio-1,3-benzothiazole (pmtbt);
4,5-dihydroxyimidazolidine-2-thione; imidazolidine-2-thione;
1,1'-thiocarbonyldiimidazole; 2,2'-dithiobis(benzothiazole); and
5,5'-dithiobis(tetrazole). N--S Valence Stabilizer #30: Examples of
six-membered heterocyclic rings containing one, two, three, or four
nitrogen atoms at least one additional sulfur atom binding site not
in a ring (N--S Bidentates, N--S Tridentates, N--S Tetradentates,
or N--S Hexadentates) that meet the requirements for use as "wide
band" valence stabilizers for Co.sup.+3 include, but are not
limited to: 4-aminomethyl-3-pyridinemethanethiol (including
thiopyridoxamine); 2-mercaptopyridine;
2-(methylthio)methylpyridine; 2-(2-(methylthio)ethyl)pyridine;
2,6-(thiomethyl)pyridine; 2,6-(methylthiomethyl)pyridine;
2,6-(methyldisulfidomethyl)pyridine; 2-mercaptopyrimidine;
2-dithiomethylpyrimidine; 2-mercaptoquinoline; 8-mercaptoquinoline
(thioxine); 8-methylthioquinoline; 2-mercaptoquinazoline;
thioorotic acid
(1,2,3,6-tetrahydro-2,6-dithiono-4-pyrimidinecarboxylic acid)
(6-thiouracilcarboxylic acid); 1-methylpyrimidine-2-thione;
2-thiouracil; 2,4-dithiouracil; 6-mercaptopurine;
bis(N,N,N',N'-tetra(2-(2-pyridyl)ethane)aminomethane)sulfide;
bis(N,N,N',N'-tetra(2-(2-pyridyl)ethane)aminomethane)disulfide;
bis(N,N,N',N'-tetra(2-(2-pyridyl)ethane)aminoethane)sulfide;
bis(N,N,N',N'-tetra(2-(2-pyridyl)ethane)aminoethane)disulfide;
1,3,5-triazine-6-thione; 2-benzylmercapto-1,3,5-triazine; triazine
dithiols [i.e., 6-(phenylamino)-1,3,5-triazine-2,4-dithiol (ptd);
6-aniline-1,3,5-triazine-2,4-dithiol (atd); and
2-(N,N-dialkylamino)-1,3,5-triazine-4,6-dithiol];
2-thioquinazoline; 2-thioquinazolin-4-one; thiomorpholin-3-thione;
[2-(aminomethyl)thio]pyridine; 6-mercaptopurine; dithiouracil; and
2,2'-dithiodipyridine (2,2'-dipyridyl disulfide). N--S Valence
Stabilizer #31: Examples of five-membered heterocyclic rings
containing one or two sulfur atoms at least one additional nitrogen
atom binding site not in a ring (N--S Bidentates, N--S Tridentates,
N--S Tetradentates, or N--S Hexadentates) that meet the
requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to: 2-aminothiophene;
2,5-diaminothiophene; 2-aminomethylthiophene;
2,5-di(aminomethyl)thiophene; 2-aminobenzothiophene; and
2-iminothiolane. N--S Valence Stabilizer #32: Examples of
six-membered heterocyclic rings containing one or two sulfur atoms
at least one additional nitrogen atom binding site not in a ring
(N--S Bidentates, N--S Tridentates, N--S Tetradentates, or N--S
Hexadentates) that meet the requirements for use as "wide band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
2-aminothiopyran; 2,6-diaminothiopyran; 2-aminomethylthiopyran;
2,6-di(aminomethyl)thiopyran; and 2-aminobenzothiopyran. N--S
Valence Stabilizer #33: Examples of five-membered heterocyclic
rings containing one, two, three, or four nitrogen atoms at least
one additional sulfur atom binding site in a separate ring (N--S
Bidentates, N--S Tridentates, N--S Tetradentates) that meet the
requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to: 2-(2-thiophene)pyrrole;
2,5-di(2-thiophene)pyrrole; 2-(2-thiopyran)pyrrole;
2,5-di(2-thiopyran)pyrrole; 2,5-di(2-pyrrole)thiophene;
2,6-di(2-pyrrole)thiopyran; and
3,5-bis(2-thienyl)-4-amino-1,2,4-triazole (2-tat). N--S Valence
Stabilizer #34: Examples of six-membered heterocyclic rings
containing one, two, three, or four nitrogen atoms at least one
additional sulfur atom binding site in a separate ring (N--S
Bidentates, N--S Tridentates, N--S Tetradentates) that meet the
requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to:
2-(2-thiadiazolyl)benzimidazole; 2-(2-thiophene)pyridine;
2,6-di(2-thiophene)pyridine; 2-(2-thiopyran)pyridine;
2,6-di(2-thiopyran)pyridine; 2,5-di(2-pyridyl)thiophene;
2,6-di(2-pyridyl)thiopyran; and 2-(4-thiazolyl)benzimidazole. N--S
Valence Stabilizer #35: Examples of two-, three-, four-, six-,
eight-, and ten-membered macrocyclics, macrobicyclics, and
macropolycyclics (including catapinands, cryptands, cyclidenes, and
sepulchrates) wherein all binding sites are composed of nitrogen
(usually amine or imine groups) or sulfur (usually thiols,
mercaptans, or thiocarbonyls) and are not contained in component
heterocyclic rings (N--S Bidentates, N--S Tridentates, N--S
Tetradentates, and N--S Hexadentates) that meet the requirements
for use as "wide band" valence stabilizers for Co.sup.+3 include,
but are not limited to: azathiacyclobutane ([4]aneNS);
azathiacyclopentane ([5]aneNS); azathiacyclohexane ([6]aneNS);
azathiacycloheptane ([7]aneNS); azathiacyclooctane ([8]aneNS);
azathiacyclobutene ([4]eneNS); azathiacyclopentene ([5]eneNS);
azathiacyclohexene ([6]eneNS); azathiacycloheptene ([7]eneNS);
azathiacyclooctene ([8]eneNS); azathiacyclobutadiene ([4]dieneNS);
azathiacyclopentadiene ([5]dieneNS); azathiacyclohexadiene
([6]dieneNS); azathiacycloheptadiene ([7]dieneNS);
azathiacyclooctadiene ([8]dieneNS); diazathiacyclohexane
([6]aneSN.sub.2); diazathiacycloheptane ([7]aneSN.sub.2);
diazathiacyclooctane ([8]aneSN.sub.2); diazathiacyclononane
([9]aneSN.sub.2); diazathiacyclodecane ([10]aneSN.sub.2);
diazathiacycloundecane ([11]aneSN.sub.2); diazathiacyclododecane
([12]aneSN.sub.2); diazathiacyclohexene ([6]eneSN.sub.2);
diazathiacycloheptene ([7]eneSN.sub.2); diazathiacyclooctene
([8]eneSN.sub.2); diazathiacyclononene ([9]eneSN.sub.2);
diazathiacyclodecene ([10]eneSN.sub.2); diazathiacycloundecene
([11]eneSN.sub.2); diazathiacyclododecene ([12]eneSN.sub.2);
diazadithiacyclooctane ([8]aneS.sub.2N.sub.2);
diazadithiacyclononane ([9]aneS.sub.2N.sub.2);
diazadithiacyclodecane ([10]aneS.sub.2N.sub.2);
diazadithiacycloundecane ([11]aneS.sub.2N.sub.2);
diazadithiacyclododecane ([12]aneS.sub.2N.sub.2);
diazadithiacyclotridecane ([13]aneS.sub.2N.sub.2);
diazadithiacyclotetradecane ([14]aneS.sub.2N.sub.2);
diazadithiacyclopentadecane ([15]aneS.sub.2N.sub.2);
diazadithiacyclohexadecane ([16]aneS.sub.2N.sub.2);
diazadithiacycloheptadecane ([17]aneS.sub.2N.sub.2);
diazadithiacyclooctadecane ([18] aneS.sub.2N.sub.2);
diazadithiacyclononadecane ([19]aneS.sub.2N.sub.2);
diazadithiacycloeicosane ([20]aneS.sub.2N.sub.2);
diazadithiacyclooctadiene ([8]dieneS.sub.2N.sub.2);
diazadithiacyclononadiene ([9]dieneS.sub.2N.sub.2);
diazadithiacyclodecadiene ([10]dieneS.sub.2N.sub.2);
diazadithiacycloundecadiene ([11]dieneS.sub.2N.sub.2);
diazadithiacyclododecadiene ([12]dieneS.sub.2N.sub.2);
diazadithiacyclotridecadiene ([13]dieneS.sub.2N.sub.2);
diazadithiacyclotetradecadiene ([14]dieneS.sub.2N.sub.2);
diazadithiacyclopentadecadiene ([15]dieneS.sub.2N.sub.2);
diazadithiacyclohexadecadiene ([16]dieneS.sub.2N.sub.2);
diazadithiacycloheptadecadiene ([17]dieneS.sub.2N.sub.2);
diazadithiacyclooctadecadiene ([18]dieneS.sub.2N.sub.2);
diazadithiacyclononadecadiene ([19]dieneS.sub.2N.sub.2);
diazadithiacycloeicosadiene ([20]dieneS.sub.2N.sub.2); and
tetramethyldithiahexaazacyclobidecanehexaene (mtab). N--S Valence
Stabilizer #36: Examples of four-, six-, eight-, or ten-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
binding sites are composed of nitrogen or sulfur and are contained
in component heterocyclic rings (N--S Bidentates, N--S Tridentates,
N--S Tetradentates, or N--S Hexadentates) that meet the
requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to: dithiopyrandipyridines;
dithiophenedipyrroles; trithiopyrantripyridines;
trithiophenetripyrroles; tetrathiopyrantetrapyridines; and
tetrathiophenetetrapyrroles. N--S Valence Stabilizer #37: Examples
of four-, six-, eight-, or ten-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all binding sites
are composed of nitrogen or sulfur and are contained in a
combination of heterocyclic rings and amine, imine, thiol,
mercapto, or thiocarbonyl groups (N--S Bidentates, N--S
Tridentates, N--S Tetradentates, or N--S Hexadentates) that meet
the requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to: azathiatetraphyrins;
diazadithiatetraphyrins; azathiahexaphyrins;
diazadithiahexaphyrins; and triazatrithiahexaphyrins. N--O Valence
Stabilizer #1: Examples of N-hydroxy(or N,N'-dihydroxy)amidines and
N-hydroxy(or N,N'-dihydroxy)diamidines (N--O bidentates, N--O
tridentates, or N--O tetradentates) that meet the requirements for
use as "wide band" valence stabilizers for Co.sup.+3 include, but
are not limited to: N-hydroxy-N,N'-dimethylformamidine;
N-hydroxy-N,N'-diethylformamidine;
N-hydroxy-N,N'-diisopropylformamidine;N-hydroxy-N,N'-dibutylformamidine;
N-hydroxy-N,N'-diphenylformamidine;
N-hydroxy-N,N'-dibenzylformamidine;
N-hydroxy-N,N'-dinaphthylformamidine;
N-hydroxy-N,N'-dicyclohexylformamidine;
N-hydroxy-N,N'-dinorbornylformamidine;
N-hydroxy-N,N'-diadamantylformamidine;
N-hydroxy-N,N'-dianthraquinonylformamidine;
N-hydroxy-N,N'-dimethylacetamidine;
N-hydroxy-N,N'-diethylacetamidine;
N-hydroxy-N,N'-diisopropylacetamidine;
N-hydroxy-N,N'-dibutylacetamidine;
N-hydroxy-N,N'-diphenylacetamidine;
N-hydroxy-N,N'-dibenzylacetamidine;
N-hydroxy-N,N'-dinaphthylacetamidine;
N-hydroxy-N,N'-dicyclohexylacetamidine;
N-hydroxy-N,N'-dinorbornylacetamidine;
N-hydroxy-N,N'-diadamantylacetamidine;
N-hydroxy-N,N'-dimethylbenzamidine;
N-hydroxy-N,N'-diethylbenzamidine;
N-hydroxy-N,N'-diisopropylbenzamidine;
N-hydroxy-N,N'-dibutylbenzamidine;
N-hydroxy-N,N'-diphenylbenzamidine;
N-hydroxy-N,N'-dibenzylbenzamidine;
N-hydroxy-N,N'-dinaphthylbenzamidine;
N-hydroxy-N,N'-dicyclohexylbenzamidine;
N-hydroxy-N,N'-dinorbornylbenzamidine;
N-hydroxy-N,N'-diadamantylbenzamidine;
N-hydroxy-N,N'-dimethyltoluamidine;
N-hydroxy-N,N'-diethyltoluamidine;
N-hydroxy-N,N'-diisopropyltoluamidine;
N-hydroxy-N,N'-dibutyltoluamidine;
N-hydroxy-N,N'-diphenyltoluamidine;
N-hydroxy-N,N'-dibenzyltoluamidine;
N-hydroxy-N,N'-dinaphthyltoluamidine;
N-hydroxy-N,N'-dicyclohexyltoluamidine;
N-hydroxy-N,N'-dinorbornyltoluamidine;
N-hydroxy-N,N'-diadamantyltoluamidine; N,N-dihydroxyoxalic
diamidine; N,N'-dihydroxymalonic diamidine; N,N'-dihydroxysuccinic
diamidine; N,N'-dihydroxyglutaric diamidine; N,N'-dihydroxyadipic
diamidine; N,N'-dihydroxypimelic diamidine; N,N'-dihydroxysuberic
diamidine; N,N'-dihydroxyphthalic diamidine;
N,N'-dihydroxyterephthalic diamidine; N,N'-dihydroxyisophthalic
diamidine; N,N'-dihydroxypiperazine diamidine. N--O Valence
Stabilizer #2: Examples of guanylureas, guanidinoureas,
bis(guanylureas), bis(guanidinoureas), poly(guanylureas), and
poly(guanidinoureas) (N--O Bidentates and N--O Tetradentates) that
meet the requirements for use as "wide band" valence stabilizers
for Co.sup.+3 include, but are not limited to: guanylurea
(amidinourea)(dicyandiamidine); guanidinourea; methylguanylurea;
ethylguanylurea; isopropylguanylurea; butylguanylurea;
benzylguanylurea; phenylguanylurea; tolylguanylurea;
naphthylguanylurea; cyclohexylguanylurea; norbornylguanylurea;
adamantylguanylurea; dimethylguanylurea; diethylguanylurea;
diisopropylguanylurea; dibutylguanylurea; dibenzylguanylurea;
diphenylguanylurea; ditolylguanylurea; dinaphthylguanylurea;
dicyclohexylguanylurea; dinorbornylguanylurea;
diadamantylguanylurea; ethylenebis(guanylurea);
propylenebis(guanylurea); phenylenebis(guanylurea);
piperazinebis(guanylurea); oxalylbis(guanylurea);
malonylbis(guanylurea); succinylbis(guanylurea);
phthalylbis(guanylurea); 2-ureidothiazole;
2-ureidooxazole; 2-ureidoimidazole; 3-ureidopyrazole;
3-ureido-1,2,4-triazole; and 5-ureidotetrazole. N--O Valence
Stabilizer #3: Examples of amidinoamides, guanidinoamides,
bis(amidinoamides), bis(guanidinoamides), poly(amidinoamides), and
poly(guanidinoamides) (including both N-amidinoamides and
2-amidinoacetamides) (N--O Bidentates, N--O Tridentates, and N--O
Tetradentates) that meet the requirements for use as "wide band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
amidinoacetamide (1-acetylguanidine); guanidinoacetamide;
amidinopropanamide; amidinobutanamide; amidinobenzamide;
amidinotoluamide; amidinocyclohexamide; N-methylamidinoacetamide;
N-ethylamidinopropanamide; N-propylamidinobutanamide;
N-phenylamidinobenzamide; N-tolylamidinotoluamide;
N-cyclohexylamidinocyclohexamide; bis(amidinooxamide);
bis(amidinomalonamide); bis(amidinosuccinamide);
bis(amidinophthalamide); 2-amidinoacetamide (malonamamidine);
N-methyl-2-amidinoacetamide; N-ethyl-2-amidinoacetamide;
N-phenyl-2-amidinoacetamide; N-benzyl-2-amidinoacetamide;
N-cyclohexyl-2-amidinoacetamide; N,N'-dimethyl-2-amidinoacetamide;
N,N'-diethyl-2-amidinoacetamide; N,N'-diphenyl-2-amidinoacetamide;
N,N'-dibenzyl-2-amidinoacetamide;
N,N'-dicyclohexyl-2-amidinoacetamide; 2-N-acylaminothiazole;
2-N-acylaminooxazole; 2-N-acylaminoimidazole;
3-N-acylaminopyrazole; 3-N-acylamino-1,2,4-triazole; and
5-N-acylaminotetrazole. N--O Valence Stabilizer #4: Examples of
imidoylamides, bis(imidoylamides), and poly(imidoylamides) (N--O
Bidentates, N--O Tridentates, and N--O Tetradentates) that meet the
requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to: acetimidoylacetamide;
acetimidoylpropanamide; acetimidoylbutanamide;
acetimidoylbenzamide; acetimidolytoluamide;
acetimidoylcyclohexamide; propimidoylpropanamide;
butimidoylbutanamide; benzimidoylbenzamide;
ethylenebis(acetimidoylacetamide);
propylenebis(acetimidoylacetamide); and
phenylenebis(acetimidoylacetamide). N--O Valence Stabilizer #5:
Examples of O-amidinocarbamates, bis(O-amidinocarbamates), and
poly(O-amidinocarbamates) (N--O Bidentates and N--O Tetradentates)
that meet the requirements for use as "wide band" valence
stabilizers for Co.sup.+3 include, but are not limited to:
O-amidinocarbamate; N-methyl-O-amidinocarbamate;
N-ethyl-O-amidinocarbamate; N-isopropyl-O-amidinocarbamate;
N-butyl-O-amidinocarbamate; N-benzyl-O-amidinocarbamate;
N-phenyl-O-amidinocarbamate; N-tolyl-O-amidinocarbamate;
N-naphthyl-O-amidinocarbamate; N-cyclohexyl-O-amidinocarbamate;
N-norbornyl-O-amidinocarbamate; N-adamantyl-O-amidinocarbamate;
N,N'-dimethyl-O-amidinocarbamate; N,N'-diethyl-O-amidinocarbamate;
N,N'-diisopropyl-O-amidinocarbamate;
N,N'-dibutyl-O-amidinocarbamate; N,N'-dibenzyl-O-amidinocarbamate;
N,N'-diphenyl-O-amidinocarbamate; N,N'-ditolyl-O-amidinocarbamate;
N,N'-dinaphthyl-O-amidinocarbamate;
N,N'-dicyclohexyl-O-amidinocarbamate;
N,N'-dinorbornyl-O-amidinocarbamate;
N,N'-diadamantyl-O-amidinocarbamate;
ethylenebis(O-amidinocarbamate); propylenebis(O-amidinocarbamate);
phenylenebis(O-amidinocarbamate);
piperazinebis(O-amidinocarbamate); oxalylbis(O-amidinocarbamate);
malonylbis(O-amidinocarbamate); succinylbis(O-amidinocarbamate);
phthalylbis(O-amidinocarbamate); 2-O-carbamatothiazole;
2-O-carbamatooxazole; 2-O-carbamatoimidazole;
3-O-carbamatopyrazole; 3-O-carbamato-1,2,4-triazole; and
5-carbamatotetrazole. N--O Valence Stabilizer #6: Examples of
S-amidinothiocarbamates, bis(S-amidinothiocarbamates), and
poly(S-amidinothiocarbamates) (N-O Bidentates and N-O
Tetradentates) that meet the requirements for use as "wide band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
S-amidinothiocarbamate; N-methyl-S-amidinothiocarbamate;
N-ethyl-S-amidinothiocarbamate; N-isopropyl-S-amidinothiocarbamate;
N-butyl-S-amidinothiocarbamate; N-benzyl-S-amidinothiocarbamate;
N-phenyl-S-amidinothiocarbamate; N-tolyl-S-amidinothiocarbamate;
N-naphthyl-S-amidinothiocarbamate;
N-cyclohexyl-S-amidinothiocarbamate;
N-norbornyl-S-amidinothiocarbamate;
N-adamantyl-S-amidinothiocarbamate;
N,N'-dimethyl-S-amidinothiocarbamate;
N,N'-diethyl-S-amidinothiocarbamate;
N,N'-diisopropyl-S-amidinothiocarbamate;
N,N'-dibutyl-S-amidinothiocarbamate;
N,N'-dibenzyl-S-amidinothiocarbamate;
N,N'-diphenyl-S-amidinothiocarbamate;
N,N'-ditolyl-S-amidinothiocarbamate;
N,N'-dinaphthyl-S-amidinothiocarbamate;
N,N'-dicyclohexyl-S-amidinothiocarbamate;
N,N'-dinorbornyl-S-amidinothiocarbamate;
N,N'-diadamantyl-S-amidinothiocarbamate;
ethylenebis(S-amidinothiocarbamate);
propylenebis(S-amidinothiocarbamate);
phenylenebis(S-amidinothiocarbamate);
piperazinebis(S-amidinothiocarbamate);
oxalylbis(S-amidinothiocarbamate);
malonylbis(S-amidinothiocarbamate);
succinylbis(S-amidinothiocarbamate);
phthalylbis(S-amidinothiocarbamate); 2-O-monothiocarbamatothiazole;
2-O-monothiocarbamatooxazole; 2-O-monothiocarbamatoimidazole;
3-O-monothiocarbamatopyrazole;
3-O-monothiocarbamato-1,2,4-triazole; and
5-O-monothiocarbamatotetrazole. N--O Valence Stabilizer #7:
Examples of diimidosulfuric acid, bis(diimidosulfuric acid), and
derivatives thereof (N--O Bidentates and N--O Tetradentates) that
meet the requirements for use as "wide band" valence stabilizers
for Co.sup.+3 include, but are not limited to: diimidosulfuric
acid; O-phenyldiimidosulfuric acid; O-benzyldiimidosulfuric acid,
O-cyclohexyldiimidosulfuric acid, O-norbornyldiimidosulfuric acid,
O,O'-diphenyldiimidosulfuric acid; O,O'-dibenzyldiimidosulfuric
acid, O,O'-dicyclohexyldiimidosulfuric acid, and
O,O'-dinorbornyldiimidosulfuric acid. N--O Valence Stabilizer #8:
Examples of phosphorimidic acid, bis(phosphorimidic acid); and
poly(phosphorimidic acid), and derivatives thereof (N--O
Bidentates, N--O Tetradentates) that meet the requirements for use
as "wide band" valence stabilizers for Co#.sup.3 include, but are
not limited to: phosphorimidic acid; O-phenylphosphorimidic acid;
O-benzylphosphorimidic acid; O-cyclohexylphosphorimidic acid;
O-norbornylphosphorimidic acid; O,O'-diphenylphosphorimidic acid;
O,O'-dibenzylphosphorimidic acid; O,O'-dicyclohexylphosphorimidic
acid; and O,O'-dinorbornylphosphorimidic acid. N--O Valence
Stabilizer #9: Examples of phosphoric triamides, bis(phosphoric
triamides), and poly(phosphoric triamides) (N--O Bidentates and
N--O Tetradentates) that meet the requirements for use as "wide
band" valence stabilizers for Co.sup.+3 include, but are not
limited to: phosphoric triamide; phosphoramidic dihydrazide;
N-phenylphosphoric triamide, N-benzylphosphoric triamide;
N-cyclohexylphosphoric triamide; N-norbornylphosphoric triamide;
N,N'-diphenylphosphoric triamide, N,N'-dibenzylphosphoric triamide;
N,N'-dicyclohexylphosphoric triamide; and
N,N'-dinorbornylphosphoric triamide. N--O Valence Stabilizer #10:
Examples of phosphoramidic acid, phosphorodiamidic acid,
bis(phosphoramidic acid), bis(phosphorodiamidic acid),
poly(phosphoramidic acid), poly(phosphorodiamidic acid), and
derivatives thereof (N--O Bidentates and N--O Tetradentates) that
meet the requirements for use as "wide band" valence stabilizers
for Co.sup.+3 include, but are not limited to: phosphoramidic acid,
phosphorodiamidic acid, phosphoramidohydrazidic acid;
phosphorohydrazidic acid; phosphorodihydrazidic acid;
O-phenylphosphoramidic acid; O-benzylphosphoramidic acid;
O-cyclohexylphosphoramidic acid; O-norbornylphosphoramidic acid;
O,O'-diphenylphosphoramidic acid; O,O'-dibenzylphosphoramidic acid;
O,O'-dicyclohexylphosphoramidic acid; and
O,O'-dinorbornylphosphoramidic acid. N--O Valence Stabilizer #11:
Examples of N-acyl 7-aminobenzylidenimines (N--O Bidentates or N--O
Tetradentates) that meet the requirements for use as "wide band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
N-acetyl 7-methylaminobenzylidenimine; N-acetyl
7-phenylaminobenzylidenimine; N-benzoyl
7-methylaminobenzylidenimine; and N-benzoyl
7-phenylaminobenzylidenimine. N--O Valence Stabilizer #12: Examples
of oximes, dioximes, and poly(oximes) (N--O Bidentates, N--O
Tridentates, and N--O Tetradentates) that meet the requirements for
use as "wide band" valence stabilizers for Co.sup.+3 include, but
are not limited to: acetaldoxime (Hado); acetoxime (acetone
oxime)(Hato); butanone oxime; pentanone oxime; hexanone oxime;
pinacolone oxime; heptanone oxime; octanone oxime; cyclopentanone
oxime; cyclohexanone oxime; cycloheptanone oxime; cyclooctanone
oxime; cyclopentanedione dioxime; cyclohexanedione dioxime;
cycloheptanedione dioxime; cyclooctanedione dioxime; isatin
dioxime; benzaldehyde oxime; naphthaldehyde oxime; norbornanone
oxime; camphor oxime; dimethylglyoxime (H.sub.2DMG);
diethylglyoxime; diisopropylglyoxime; ditertbutylglyoxime;
dicyanoglyoxime; dicyanamidoglyoxime; diphenylglyoxime (Hdfg);
dibenzylglyoxime; dicyclohexylglyoxime; dinorbornylglyoxime;
camphorquinone dioxime (Hcqd); nopinoquinone dioxime (Hnqd);
butyraldoxime; propionaldoxime; furildioxime; and thienyldioxime.
N--O Valence Stabilizer #13: Examples of carbonyl oximes,
bis(carbonyl oximes), and poly(carbonyl oximes) (N--O Bidentates,
N--O Tridentates, and N--O Tetradentates) that meet the
requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to: diacetyl monoxime
(2,3-butanedione monoxime); benzil monoxime
(1,2-diphenylethanedione monoxime);
1,2-dicyclohexylethanedionemonoxime;
1,2-(trifluoromethyl)ethanedionemonoxime;
1,2-dinorbornylethanedione monoxime; cyclopentanedione monoxime;
cyclohexanedione monoxime; cycloheptanedione monoxime;
cyclooctanedione monoxime; camphorquinone oxime;
3-hydroxyiminopentane-2,4-dione; and 4-isonitrosopyralozone. N--O
Valence Stabilizer #14: Examples of imine oximes, bis(imine
oximes), and poly(imine oximes) (including 2-nitrogen heterocyclic
oximes) (N--O Bidentates, N--O Tridentates, N--O Tetradentates, and
N--O Hexadentates) that meet the requirements for use as "wide
band" valence stabilizers for Co.sup.+3 include, but are not
limited to: 3-(methylimino)butan-2-one oxime;
4-(methylimino)hexan-3-one oxime;
1,2-diphenyl-2-(methylimino)ethan-1-one oxime;
1,2-diphenyl-2-(phenylimino)ethan-1-one oxime;
1,2-dicyclohexyl-2-(methylimino)ethan-1-one oxime;
1,2-dicyclohexyl-2-(cyclohexylimino)ethan-1-one oxime;
1,2-dinorbornyl-2-(methylimino)ethan-1-one oxime;
N,N'-methylenebis-(3-iminobutan-2-one oxime);
N,N'-methylenebis-(4-iminohexan-3-one oxime);
N,N'-methylenebis-(1,2-diphenyl-2-iminoethan-1-one oxime);
N,N'-methylenebis-(1,2-dicyclohexyl-2-iminoethan-1-one oxime);
N,N'-methylenebis-(1,2-dinorbornyl-2-iminoethan-1-one oxime);
N,N'-ethylenebis-(3-iminobutan-2-one oxime);
N,N'-ethylenebis-(4-iminohexan-3-one oxime);
N,N'-ethylenebis-(1,2-diphenyl-2-iminoethan-1-one oxime);
N,N'-ethylenebis-(1,2-dicyclohexyl-2-iminoethan-1-one oxime);
N,N'-ethylenebis-(1,2-dinorbornyl-2-iminoethan-1-one oxime);
N,N'-propylenebis-(3-iminobutan-2-one oxime);
N,N'-propylenebis-(4-iminohexan-3-one oxime);
N,N'-propylenebis-(1,2-diphenyl-2-iminoethan-1-one oxime);
N,N'-propylenebis-(1,2-dicyclohexyl-2-iminoethan-1-one oxime);
N,N'-propylenebis-(1,2-dinorbornyl-2-iminoethan-1-one oxime);
diacetylazine oxime (Hazio); 2-pyridinaldoxime (Hpao); methyl
2-pyridyl ketone oxime; ethyl 2-pyridyl ketoxime; phenyl 2-pyridyl
ketone oxime (Hppk); benzyl 2-pyridyl ketoxime; di(2-pyridyl)
ketone oxime; methyl 2-pyrrolyl ketone oxime; ethyl 2-pyrrolyl
ketone oxime; phenyl 2-pyrrolyl ketone oxime; di(2-pyrrolyl) ketone
oxime; and tris(2-aldoximo-6-pyridyl)phosphine. N--O Valence
Stabilizer #15: Examples of hydroxy oximes, bis(hydroxy oximes),
and poly(hydroxy oximes) (including 2-oxygen heterocyclic oximes)
(N--O Bidentates, N--O Tridentates, N--O Tetradentates, and N--O
Hexadentates) that meet the requirements for use as "wide band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
3-hydroxybutan-2-one oxime; 4-hydroxyhexan-3-one oxime; benzoin
oxime (bo)(1,2-diphenyl-2-hydroxyethanone oxime);
1,2-di(trifluoromethyl)-2-hydroxyethanone oxime;
1,2-dicyclohexyl-2-hydroxyethanone oxime;
1,2-dinorbornyl-2-hydroxyethanone oxime; salicylaldoxime
(so)(saldox); 2-hydroxy-1-naphthaldehyde oxime; 2-furanaldoxime;
furildioxime; methyl 2-furanyl ketone oxime; ethyl 2-furanyl
ketoxime; phenyl 2-furanyl ketone oxime; benzyl 2-furanyl ketoxime;
di(2-furanyl) ketone oxime; and 2,5-(oximinomethyl)phenol. N--O
Valence Stabilizer #16: Examples of amino oximes, bis(amino
oximes), and poly(amino oximes) (N--O Bidentates, N--O Tridentates,
N--O Tetradentates, and N--O Hexadentates) that meet the
requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to:
3-(methylamino)butan-2-one oxime (HMeabo);
4-(methylamino)hexan-3-one oxime (HEtabo);
1,2-diphenyl-2-(methylamino)ethanone oxime (HPhabo);
1,2-diphenyl-2-(phenylamino)ethanone oxime;
1,2-dicyclohexyl-2-(methylamino)ethanone oxime (HcyHxabo);
1,2-dicyclohexyl-2-(cyclohexylamino)ethanoneoxime;
1,2-di(trifluoromethyl)-2-(methylamino)ethanoneoxime;
1,2-dinorbornyl-2-(methylamino)ethanone oxime (HNorbabo);
N,N'-ethylenebis-(3-aminobutan-2-one oxime)(Haboen);
N,N'-ethylenebis-(4-aminohexan-3-one oxime);
N,N'-ethylenebis-(1,2-diphenyl-2-aminoethanone oxime);
N,N'-ethylenebis-(1,2-dicyclohexyl-2-aminoethanone oxime);
N,N'-ethylenebis-(1,2-di(trifluoromethyl)-2-aminoethanone oxime);
N,N'-ethylenebis-(1,2-dinorbornyl-2-aminoethanone oxime);
N,N'-propylenebis-(3-aminobutan-2-one oxime)(Habopn);
N,N'-propylenebis-(4-aminohexan-3-one oxime);
N,N'-propylenebis-(1,2-diphenyl-2-aminoethanone oxime);
N,N'-propylenebis-(1,2-dicyclohexyl-2-aminoethanone oxime);
N,N'-propylenebis-(1,2-di(trifluoromethyl)-2-aminoethanone oxime);
N,N'-propylenebis-(1,2-dinorbornyl-2-aminoethanone oxime);
2,2'-iminobis(acetamidoxime); 1-diethylamino-3-butanoxime; and
di-2-pyridyl ketone oxime. N--O Valence Stabilizer #17: Examples of
amido oximes, bis(amido oximes), and poly(amido oximes) (N--O
Bidentates, N--O Tridentates, N--O Tetradentates, and N--O
Hexadentates) that meet the requirements for use as "wide band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
formamide oxime; acetamide oxime; propanamide oxime; butanamide
oxime; benzamide oxime (Hbamox); naphthamide oxime; diformamide
dioxime; salicylamide oxime; and 4-imidazolamide oxime. N--O
Valence Stabilizer #18: Examples of azo oximes, bis(azo oximes),
and poly(azo oximes) (N--O Bidentates, N--O Tridentates, N--O
Tetradentates, and N--O Hexadentates) that meet the requirements
for use as "wide band" valence stabilizers for Co.sup.+3 include,
but are not limited to: acetaldehyde phenylhydrazone oxime;
propionaldehyde phenylhydrazone oxime; and benzaldehyde
phenylhydrazone oxime. Also includes hydrazone oximes. N--O Valence
Stabilizer #19: Examples of 2-nitrosophenols (o-quinone monoximes)
(N--O Bidentates) that meet the requirements for use as "wide band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
2-nitrosophenol; 1-nitroso-2-naphthol (Honn); 2-nitroso-1-naphthol
(Htnn); 3-nitrosopyrocatechol; 3,6-dinitrosopyrocatechol;
2-nitrosoresorcinol; 2,4-dinitrosoresorcinol;
2,4,6-trinitrosoresorcinol; 2-nitrosohydroquinone;
2,6-dinitrosohydroquinone; 2,3,5,6-tetranitrosohydroquinone;
4-nitrosopyrogallol; 4,6-dinitrosopyrogallol;
2-nitrosophloroglucinol; 2,4,6-trinitrosophloroglucinol;
7-nitroso-6-hydroxyindazole; Pigment Green 12 (C.I. 10020);
Naphthol Green; and nitroso-R-salt. N--O Valence Stabilizer #20:
Examples of 2-nitrophenols (N--O Bidentates) that meet the
requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to: 2-nitrophenol;
2,3-dinitrophenol; 2,4-dinitrophenol; 2,5-dinitrophenol;
2,6-dinitrophenol; 2,4,6-trinitrophenol (picric acid);
2-amino-4,6-dinitrophenol (picramic
acid); 1-nitro-2-naphthol; 2-nitro-1-naphthol; 3-nitropyrocatechol;
3,6-dinitropyrocatechol; 2-nitroresorcinol; 2,4-dinitroresorcinol;
2,4,6-trinitroresorcinol (styphnic acid); 2-nitrohydroquinone;
2,6-dinitrohydroquinone; 2,3,5,6-tetranitrohydroquinone;
4-nitropyrogallol; 4,6-dinitropyrogallol; 2-nitrophloroglucinol;
2,4,6-trinitrophloroglucinol; dinitrocresol;
7-nitro-6-hydroxyindazole; Dinoseb; Eosin; Naphthol Yellow; and
Martius Yellow. N--O Valence Stabilizer #21: Examples
ofbydroxamates (hydroxylamines), bis(hydroxamates), and
poly(hydroxamates) (N--O Bidentates, N--O Tetradentates, and N--O
Hexadentates) that meet the requirements for use as "wide band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
acetohydroxamic acid; propianohydroxamic acid; butyrohydroxamic
acid; crotonohydroxamic acid; sorbohydroxamic acid; benzohydroxamic
acid (BH.sub.2); toluichydroxamic acid; salicylhydroxamic acid
(SH.sub.2); phenylacetohydroxamic acid (PhH.sub.2);
anthranilhydroxamic acid (AnH.sub.2); nicotinehydroxamic acid
(NiCH.sub.2); picolinehydroxamic acid; cyclohexanehydroxamic acid
(CH.sub.2); quinoline 8-hydroxamic acid (QH.sub.2);
cinnamylhydroxamic acid (CnH.sub.2); oxaldihydroxamic acid
(OxalH.sub.2); succinylbis-N-phenylhydroxamic acid (SuH.sub.2);
adipylbis-N-phenylhydroxamic acid (AdH.sub.2); glyoxalhydroxamic
acid (GH.sub.2); 2-thiophenecarbohydroxamic acid; thenoylhydroxamic
acid; N-phenylbenzohydroxamic acid; N-tolylbenzohydroxamic acid;
N-phenylacetohydroxamic acid; N-phenyl-2-thenoylhydroxamic acid;
N-tolyl-2-tbenoylhydroxamic acid; and polyhydroxamic acids. N--O
Valence Stabilizer #22: Examples of N-nitrosohydroxylamines,
bis(N-nitrosohydroxylamines), and poly(N-nitrosohydroxylamines)
(N--O Bidentates, N--O Tetradentates, and N--O Hexadentates) that
meet the requirements for use as "wide band" valence stabilizers
for Co.sup.+3 include, but are not limited to:
N-nitrosophenylhydroxylamine (cupferron);
N-nitrosonaphthylhydroxylamine (neocupferron);
N-nitrosoanthracylhydroxylamine; N-nitroso(2-pyridyl)hydroxylamine;
and N-nitroso(2-thiophenyl)hydroxylamine. N--O Valence Stabilizer
#23: Examples of amino acids, ortho-aminocarboxylic acids,
peptides, polypeptides, and proteins [N--O Bidentates, N--O
Tridentates, and N--O Tetradentates; possibly S--O dentates for
sulfur-contg. examples such as penicillamine and cystine] that meet
the requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to: alanine (Ala); arginine
(Arg); asparagine (Asn); aspartic acid (Asp); cysteine (Cys);
cystine (Cys or Cys.Cys); dihydroxyphenylalanine (Dopa); glutamic
acid (Glu); glutamine (Gin); glycine (Gly); histidine (His);
isoleucine (Ile); leucine (Leu); lysine (Lys); methionine (Met);
penicillamine (Pen); phenylalanine (Phe); tolylalanine (tala);
proline (Pro); sarcosine; serine (Ser); threonine (Thr); tryptophan
(Trp); tyrosine (Tyr); and valine (Val) as amino acid examples;
2-pyridinecarboxylic acid (picolinic acid), 2-pyrazinecarboxylic
acid, 2,3-dicarboxypyrazine, and anthranilic acid as
ortho-aminocarboxylic acid examples; Gly-GluO; Hgly-Gly; Gly-MetO;
Met-GlyO; Gly-TyrO; Ala-H is O; Gly-His-GlyO; Gly-Gly-His;
Gly-Leu-TyrO; penta-GlyO; His-His; triaminoisobutyrate; tetra-GlyO;
Pro-Gly; and Gly-Met as peptide examples; and azurin, carbonic
anhydrase C; carboxypeptidase; concanavalin A; cytochrome b;
cytochrome c; erythrocruorin; ferredoxin; haemerythrin;
haemoglobin; myoglobin; parvalbumin; albumin; plastocyanin;
rubredoxin; superoxide dismutase; thermolysin; and trysin as
protein examples; N-acylamino acids; aminocaproic acid; and
3,5-diiodotyrosine. N--O Valence Stabilizer #24: Examples of
amides, bis(amides), and poly(amides), including lactams (N--O
bidentates, N--O tridentates, and N--O tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: acetamide; propionamide;
butanamide; benzamide (benzoylamide)(1-phenylformamide);
1-naphthylformamide; toluamide; 1-cyclohexylformamide);
1-norbornylformamide; 1-adamantylformamide; N,N-dimethylformamide
(DMF)(DMFA); N,N-dimethylacetamide (DMAC); N,N-dimethylbenzamide;
N,N-diethylformamide; N,N-diethylacetamide; decanamide;
dodecanamide; tetradecanamide; hexadecanamide; octadecanamide;
lactobionic acid amide; (hydroxyalkylthio)succinamides;
(mercaptoalkoxy)succinamides; polycaproamides; glycinamide;
aminoalkylanilides; amidopolyamines (apa); bis(1-phenylethylamide);
oxalic semiamide; malonic semiamide; succinic semiamide;
bis(1,1'-benzotriazolyl)dicarboxamide; nicotinamide; acetanilide
(N-phenylacetamide); formanilide (N-phenylformamide); benzanilide
(N-phenylbenzamide); N-methylformanilide; acetanilide;
nicotinanilide; 4'-hydroxyacetanilide (acetaminophen);
2-pyrrolidone; methyl-2-pyrrolidone (NMP); 2-piperidone
(valerolactam); caprolactam; polymethylenepolyamine dipropionamide;
polyacrylamides; polypyrrolidones [including polyvinylpyrrolidone
(povidone)(PVP)]; pyrazolidinones; pyrazolones; diazepinones;
N-alkylazaalkene lactams; and N-(2-hydroxyalkyl)azaalkene lactams.
N--O Valence Stabilizer #25: Examples of semicarbazones,
bis(semicarbazones), and poly(semicarbazones) (N--O Bidentates,
N--O Tetradentates, and N--O Hexadentates) that meet the
requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to: acetaldehyde
semicarbazone; acetone semicarbazone; pinacolone semicarbazone;
benzaldehyde semicarbazone; naphthaldehyde semicarbazone;
norbornanone semicarbazone; camphor semicarbazone; nopinone
semicarbazone; 2-pyridinaldehyde semicarbazone; salicylaldehyde
semicarbazone; quinolinaldehyde semicarbazone; isatin
disemicarbazone; camphorquinone disemicarbazone; camphorquinone
disemicarbazone; picolinaldehyde semicarbazone; dipyridyl glyoxal
disemicarbazone; di-2-pyridyl ketone semicarbazone;
methyl-2-pyridyl ketone semicarbazone; glyoxal disemicarbazone;
acetophenone semicarbazone; biacetyl monoxime semicarbazone;
acetamidobenzaldehyde semicarbazone; thymolaldosemicarbazone;
thiophene-2-aldehyde semicarbazone; phthalaldehyde disemicarbazone;
phthalimide disemicarbazone; furaldehyde semicarbazone;
naphthoquinone semicarbazone; phenanthrequinone semi carbazone;
cyclohexanedione disemicarbazone; ionone semicarbazone;
bissemicarbazone of diethyl-3,4-dioxadioate; and lawsone
semicarbazone. N--O Valence Stabilizer #26: Examples of acyl
hydrazones, bis(acyl hydrazones), and poly(acyl hydrazones) (N--O
Bidentates, N--O Tetradentates, and N--O Hexadentates) that meet
the requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to: acetaldehyde
N-formylhydrazone; acetaldehyde N-benzoylhydrazone; acetone
N-formylhydrazone; acetone N-benzoylhydrazone; pinacolone
N-formylhydrazone; pinacolone N-benzoylhydrazone; benzaldehyde
N-formylhydrazone; benzaldehyde N-benzoylhydrazone; naphthaldehyde
N-formylhydrazone; naphthaldehyde N-benzoylhydrazone; norbornanone
N-formylhydrazone; norbornanone N-benzoylhydrazone; camphor
N-formylhydrazone; camphor N-benzoylhydrazone; nopinone
N-formylhydrazone; nopinone N-benzoylhydrazone; 2-pyridinaldehyde
N-formylhydrazone; 2-pyridinaldehyde N-benzoylhydrazone;
salicylaldehyde N-formylhydrazone; salicylaldehyde
N-benzoylhydrazone; quinolinaldehyde N-formylhydrazone;
quinolinaldehyde N-benzoylhydrazone; furan-2-aldehyde
N-formylhydrazone; furan-2-aldehyde N-benzoylhydrazone;
naphthoquinone N-formylhydrazone; naphthoquinone
N-benzoylhydrazone; ionone N-formylhydrazone; ionone
N-benzoylhydrazone; lawsone N-formylhydrazone; and lawsone
N-benzoylhydrazone. N--O Valence Stabilizer #27: Examples of
carbazones (diazenecarboxylic hydrazides), bis(carbazones), and
poly(carbazones) (N--O Bidentates, N--O Tetradentates, and N--O
Hexadentates) that meet the requirements for use as "wide band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
diphenylcarbazone; 2-phenylcarbazone; dinaphthylcarbazone; and
2-naphthylcarbazone. N--O Valence Stabilizer #28: Examples of azo
compounds with hydroxyl or carboxy or carbonyl substitution at the
ortho- (for aryl) or alpha- or beta- (for alkyl) positions,
Bis[o-(HO--) or alpha- or beta-(HO--)azo compounds], or
Poly[o-(HO--) or alpha- or beta-(HO--)azo compounds) (N--O
Bidentates, N--O Tridentates, N--O Tetradentates, or N--O
Hexadentates) that meet the requirements for use as "wide band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
2-hydroxyazobenzene [1-(phenylazo)-2-phenol];
2,2'-dihydroxyazobenzene (o,o'-dihydroxyazobenzene);
(2-furan)azobenzene; Direct Blue 2B;
1-(4-nitrophenylazo)-2-naphthol; 1-(2-hydroxyphenylazo)-2-naphthol;
1-(2-methoxyphenylazo)-2-naphthol; pyridineazo-2-naphthol (PAN);
pyridineazoresorcinol (PAR);
1-phenyl-4-(2-hydroxyphenylazo)-5-pyrazolone;
1-phenyl-4-(2-methoxyphenylazo)-5-pyrazolone;
o-hydroxy-o'-(beta-aminoethylamino)azobenzene;
2-hydroxy-2'-methoxymethyleneoxyazobenzene; methyl red; turquoise
blue (reactive blue); sunset yellow; amaranth; tartrazine;
Eriochrome Black T; tropeolins; Allura Red; amaranth; Acid Alizarin
Violet N; Acid Blue 29; Acid Orange 8, 63, and 74; Acid Red 1, 4,
8, 37, 88, 97, 114, 151, and 183; Acid Violet 7; Acid Yellow 25,
29, 34, 42, 76, and 99; Brilliant Black BN; Brilliant Crocein;
Bordeaux R; Calcion; Chicago Sky Blue; Chromotrope; Cibacron
Brilliant Red; Cibacron Brilliant Yellow; Crocein Orange; Crystal
Scarlet; Calmagite; Direct Blue 71; Direct Red 23, 80, and 81;
Direct Violet 51; Direct Yellow 8 and 27; Fast Black; Flavazin;
Mordant Blue 9; Mordant Brown 1 and 33; Napthol Blue Black; New
Coccine; Nitrazine Yellow; Nitrosulfonazo III; Orange II; Orange G,
OT, and B; Ponceau 3R and SX; Polar Yellow; 2-oxazolylazobenzene;
and 2-benzoxazolylazobenzene. N--O Valence Stabilizer #29: Examples
of diazeneformamides, diazeneacetamides, bis(diazeneformamides),
bis(diazeneacetamides), poly(diazeneformamides), and
poly(diazeneacetamides) (N--O Bidentates, N--O Tetradentates, and
N--O Hexadentates) that meet the requirements for use as "wide
band" valence stabilizers for Co.sup.+3 include, but are not
limited to: diazeneformamide, diazeneacetamide,
phenyldiazeneformamide, diphenyldiazeneformamide,
phenyldiazeneacetamide, and diphenyldiazeneacetamide. N--O Valence
Stabilizer #30: Examples of diazeneformic acids, diazeneacetic
acids, bis(diazeneformic acids), bis(diazeneacetic acids),
poly(diazeneformic acids), poly(diazeneacetic acids) and
derivatives thereof (N--O Bidentates, N--O Tetradentates, N--O
Hexadentates) that meet the requirements for use as "wide band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
diazeneformic acid, diazeneacetic acid, phenyldiazeneformic acid,
diphenyldiazeneformic acid, phenyldiazeneacetic acid, and
diphenyldiazeneacetic acid. N--O Valence Stabilizer #31: Examples
of diazeneformaldehydes, diazeneacetaldehydes,
bis(diazeneformaldehydes), bis(diazeneacetaldehydes),
poly(diazeneformaldehydes), and poly(diazeneacetaldehydes) (N--O
Bidentates, N--O Tetradentates and N--O Hexadentates) that meet the
requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to: diazeneformaldehyde,
diazeneacetaldehyde, phenyldiazeneformaldehyde,
diphenyldiazeneformaldehyde, phenyldiazeneacetaldehyde, and
diphenyldiazeneacetaldehyde. N--O Valence Stabilizer #32: Examples
of diazenediformamides, diazenediacetamides,
bis(diazenediformamides), bis(diazenediacetamides),
poly(diazenediformamides), and poly(diazenediacetamides) (N--O
Tridentates and N--O Hexadentates) that meet the requirements for
use as "wide band" valence stabilizers for Co.sup.+3 include, but
are not limited to: diazenediformamide, diazenediacetamide,
diphenydiazenediformamide, tetraphenyldiazenediformamide,
diphenyldiazenediacetamide, and tetraphenyldiazenediacetamide. N--O
Valence Stabilizer #33: Examples of diazenediformic acids,
diazenediacetic acids, bis(diazenediformic acids),
bis(diazenediacetic acids), poly(diazenediformic acids),
poly(diazenediacetic acids) and derivatives thereof (N--O
Tridentates and N--O Hexadentates) that meet the requirements for
use as "wide band" valence stabilizers for Co.sup.+3 include, but
are not limited to: diazenediformic acid, diazenediacetic acid,
phenyldiazenediformic acid, diphenyldiazenediformic acid,
phenyldiazenediacetic acid, and diphenyldiazenediacetic acid. N--O
Valence Stabilizer #34: Examples of diazenediformaldehydes,
diazenediacetaldehydes, bis(diazenediformaldehydes),
bis(diazenediacetaldehydes), poly(diazenediformaldehydes), and
poly(diazenediacetaldehydes) (N--O Tridentates and N--O
Hexadentates) that meet the requirements for use as "wide band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
diazenediformaldehyde, diazenediacetaldehyde,
diphenyldiazenediformaldehyde, and diphenyldiazenediacetaldebyde.
N--O Valence Stabilizer #35: Examples of ortho-hydroxy (or
-carboxy) substituted formazans, bis(o-hydroxy or -carboxy
substituted formazans), and poly(o-hydroxy or -carboxy substituted
formazans) (N--O Bidentates, N--O Tridentates, N--O Tetradentates,
and N--O Hexadentates) that meet the requirements for use as "wide
band" valence stabilizers for Co.sup.+3 include, but are not
limited to: 1-(2-hydroxyphenyl)-3,5-diphenylformazan;
1-(2-methoxyphenyl)-3,5-diphenylformazan;
1,5-bis(2-hydroxyphenyl)-3-phenylformazan; and
5-bis(2-methoxyphenyl)-3-phenylformazan. N--O Valence Stabilizer
#36: Examples of ortho-hydroxy (or -carboxy) substituted azines
(including ketazines), bis(o-hydroxy or carboxy substituted
azines), and poly(o-hydroxy or carboxy substituted azines) (N--O
Bidentates, N--O Tridentates, N--O Tetradentates, and N--O
Hexadentates) that meet the requirements for use as "wide band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
2-hydroxy-1-benzalazine; 2-hydroxy-1-naphthalazine; and
2-hydroxy-1-cyclohexanonazine. N--O Valence Stabilizer #37:
Examples of Schiff Bases with one Imine (C.dbd.N) Group and with
ortho- or alpha- or beta-hydroxy or carboxy or carbonyl
substitution (N--O Bidentates, N--O Tridentates, N--O
Tetradentates, N--O Pentadentates, or N--O Hexadentates) that meet
the requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to: N
-(Salicylaldehydo)isopropylamine; N-(2-Furfuralo)isopropylamine;
N-(2-Acetylfurano)isopropylamine;
N-(2-Hydroxyacetophenono)isopropylamine;
N-(Pyridoxalo)isopropylamine; N-(Salicylaldehydo)cyclohexylamine;
N-(2-Furfuralo)cyclohexylamine; N-(2-Acetylfurano)cyclohexylamine;
N-(2-Hydroxyacetophenono)cyclohexylamine;
N-(Pyridoxalo)cyclohexylamine; N-(Salicylaldehydo)aniline;
N-(2-Furfuralo)aniline (Stenhauz salt); N-(2-Acetylfurano)aniline;
N-(2-Hydroxyacetophenono)aniline; N-(Pyridoxalo)aniline;
N-(Salicylaldehydo)aminonorbornane; N-(2-Furfuralo)aminonorbornane;
N-(2-Acetylfurano)aminonorbornane;
N-(2-Hydroxyacetophenono)aminonorbornane;
N-(Pyridoxalo)aminonorbornane; (Salicylaldehydo)anisidine;
2-salicylideneiminobenzothiazole; (Salicylaldehydo)sulfamethazine;
N'-histidine-3-methoxysalicylidenimine (V-his);
N-(o-carboxybenzaldehydo)-2-aminophenol; N-(salicylaldehydo)isatin;
N-(2-furfuralo)isatin; N-(2-acetylfurano)isatin;
N-(pyridoxalo)isatin; N-(2-hydroxyacetophenono)isatin;
hydrofuramide; 2-furancarboxaldehyde phenylhydrazone;
2-furancarboxaldehyde 2-pyridyl hydrazone; salicylaldehyde
phenylhydrazone; and salicylaldehyde 2-pyridyl hydrazone. Also
includes hydrazones with ortho-O substitution. N--O Valence
Stabilizer #38: Examples of Schiff Bases with two Imine (C.dbd.N)
Groups and with ortho- or alpha- or beta-hydroxy or carboxy or
carbonyl substitution (N--O Tridentates, N--O Tetradentates, N--O
Pentadentates, or N--O Hexadentates) that meet the requirements for
use as "wide band" valence stabilizers for Co.sup.+3 include, but
are not limited to:
N,N'-(2,5-Furandicarboxaldehydo)diisopropylamine;
N,N'-(2,5-Furandicarboxaldehydo)dicyclohexylamine;
N,N'-(2,5-Furandicarboxaldehydo)dianiline;
N,N'-(2,5-Furandicarboxaldehydo)di-aminonorbornane;
N,N'-(o-Hydroxyphthalicdialdehydo)diisopropylamine;
N,N'-(o-Hydroxyphthalicdialdehydo)dicyclohexylamine;
N,N'-(o-Hydroxyphthalicdialdehydo)dianiline;
N,N'-(o-Hydroxyphthalicdialdehydo)di-aminonorbornane;
N,N'-(o-Hydroxyformylcamphoro)diisopropylamine;
N,N'-(o-Hydroxyformylcamphoro)dicyclohexylamine;
N,N'-(o-Hydroxyformylcamphoro)dianiline;
N,N'-(o-Hydroxyformylcamphoro)di-aminonorbornane;
N,N'-(o-Hydroxydiacetylbenzeno)diisopropylamine;
N,N'-(o-Hydroxydiacetylbenzeno)dicyclohexylamine;
N,N'-(o-Hydroxydiacetylbenzeno)dianiline;
N,N'-(o-Hydroxydiacetylbenzeno)di-aminonorbornane;
N,N'-(3,6-Dihydroxy-1,2-cyclohexanono)diisopropylamine;
N,N'-(3,6-Dihydroxy-1,2-cyclohexanono)dicyclohexylamine;
N,N'-(3,6-Dihydroxy-1,2-cyclohexanono)dianiline;
N,N'-(3,6-Dihydroxy-1,2-cyclohexanono)di-aminonorbornane;
N,N'-(2,5-Diacetylfurano)diisopropylamine;
N,N'-(2,5-Diacetylfurano)dicyclohexylamine;
N,N'-(2,5-Diacetylfurano)dianiline;
N,N'-(2,5-Diacetylfurano)di-aminonorbornane;
N,N'-(Salicylaldehydo)ethylenediamine;
N,N'-(o-Hydroxynaphthaldehydo)ethylenediamine;
N,N'-(o-Hydroxyacetophenono)ethylenediamine;
N,N'-(Salicylaldehydo)trimethylenediamine;
N,N'-(o-Hydroxynaphthaldehydo)trimethylenediamine;
N,N'-(o-Hydroxyacetophenono)trimethylenediamine;
N,N'-(Salicylaldehydo)cyclohexane-1,2-diamine;
N,N'-(o-Hydroxynaphthaldehydo)cyclohexane-1,2-diamine;
N,N'-(o-Hydroxyacetophenono)cyclohexane-1,2-diamine;
N,N'-(Salicylaldehydo)-1,2-diaminobenzene;
N,N'-(o-Hydroxynaphthaldehydo)-1,2-diaminobenzene;
N,N'-(o-Hydroxyacetophenono)-1,2-diaminobenzene;
N,N'-bis(salicylaldehydo)-1,12-diaminododecane (Saldn);
N,N'-bis(3-methoxysalicylaldehydo)-o-phenyldiamine;N,N'-bis(3,4-difluorob-
enzaldehydo)-4,4'-benzidine; and
N,N'-phenylenebis(3-methoxysalicylidenimine) (V-ph-V). Also
includes hydrazones with ortho-O substitution. N--O Valence
Stabilizer #39: Examples of Schiff Bases with three Imine (C.dbd.N)
Groups and with ortho- or alpha- or beta-hydroxy or carboxy or
carbonyl substitution (N--O Tetradentates, N--O Pentadentates, or
N--O Hexadentates) that meet the requirements for use as "wide
band" valence stabilizers for Co.sup.+3 include, but are not
limited to: N,N',N''-(Salicylaldehydo)tris(2-aminoethyl)amine;
N,N',N''-(o-Hydroxynaphthaldehydo)tris(2-aminoethyl)amine; and
N,N',N''-(o-Hydroxyacetophenono)tris(2-aminoethyl)amine. Also
includes hydrazones with ortho-O substitution. N--O Valence
Stabilizer #40: Examples of silylaminoalcohols (N--O Bidentates,
N--O Tridentates, N--O Tetradentates, and N--O Hexadentates) that
meet the requirements for use as "wide band" valence stabilizers
for Co.sup.+3 include, but are not limited to: silatranes. N--O
Valence Stabilizer #41: Examples of hydroxyalkyl imines (imino
alcohols) (N--O Bidentates, N--O Tridentates, N--O Tetradentates,
and N--O Hexadentates) that meet the requirements for use as "wide
band" valence stabilizers for Co.sup.+3 include, but are not
limited to: 2-hydroxycyclohexylimine; 3-hydroxy-2-iminonorbornane;
2,2'-diiminodicyclohexyl ether; oxamide;
3-imino-1,5-pentanedialdehyde; iminodiacetic acid; and
iminodipropionic acid. N--O Valence Stabilizer #42: Examples of
hydroxyaryl amines and hydroxyaryl imines (N--O Bidentates, N--O
Tridentates, N--O Tetradentates, and N--O Hexadentates) that meet
the requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to: 2-aminophenol;
2-aminobenzoic acid (anthranilic acid); 2-aminoanisole;
o-phenetidine; o-anisidine; 2-hydroxymethyl)-alpha-aminotoluene;
1-amino-2-naphthol; 2-amino-1-naphthol;
2,2'-di(aminomethyl)diphenylketone; isophoronediamine;
tris-2,4,6-dimethylaminomethyl phenol; di(2-amino)phenyl ether;
1,3-di(2-amino)phenyl-2-hydroxypropane;
1,3-di(3-amino)phenyl-2-hydroxypropane;
1,3-di(2-hydroxy)phenyl-2-aminopropane;
1,3-di(3-hydroxy)phenyl-2-aminopropane;
2,2'-dihydroxyiminodibenzyl; 2,2'-iminodibenzoic acid;
2,2'-dihydroxyiminostilbene; poly(o-phenetidine);
poly(o-aminophenol); poly(o-anisidine); and
3-(anilino)propionamide. N--O Valence Stabilizer #43: Examples of
five-membered heterocyclic rings containing one, two, three, or
four nitrogen atoms at least one additional oxygen atom binding
site not in a ring (N--O Bidentates, N--O Tridentates, N--O
Tetradentates, or N--O Hexadentates) that meet the requirements for
use as "wide band" valence stabilizers for Co.sup.+3 include, but
are not limited to: 2-hydroxypyrrole;
2-(methylhydroxy)methylpyrrole; 2,5-(hydroxymethyl)pyrrole;
2,5-(methylhydroxymethyl)pyrrole; imidazoline-2-one
(2-hydroxyimidazole); 2-hydroxythiazoline; 2-hydroxybenzimidazole;
2-hydroxybenzothiazole; 2-hydroxybenzoxazole; 2-hydantoin;
di-2-pyridylglyoxal (2,2'-pyridil); bis((1-pyrazolyl)methane)ether;
bis(2-(1-pyrazolyl)ethane)ether; bis(benzimidazolylmethane)ether;
bis(benzimidazolylethane)ether; tris(imidazolyl)methanol;
tris(imidazolylmethane)methanol;
N-hydroxymethyl-N,N-(benzimidazolylmethane)amine;
N-(2-hydroxyethyl)-N,N-(benzimidazolylmethane)amine;
N,N'-di(benzimidazolylmethane)-1,3-di amino-2-hydroxypropane;
N,N,N',N'-tetrakis(benzimidazolylmethane)-1,3-diamino-2-hydroxypropane;
bis(N,N-((4-imidazolyl)methane)2-aminoethane)ether;
4-carboxybenzotriazole; antipyrine; 4-aminoantipyrine (aap);
hydantoin; aminoalkylhydantoins; 2,5-oxazolidinedione;
benzyldibenzoyltriazole (bdbt); 5-hydroxymethylimidazole;
dicarboxyalkylbenzotriazoles; bis(hydroxyphenyl)aminotriazoles;
pyrrole-2-carboxaldehyde; (oxopyrrolidinylalkyl)triazoles;
alkoxybenzotriazoles; aryloxybenzotriazoles;
3-salicylamido-4,5-dihydro-1,2,4-triazole; 5-(alkoxy)benzotriazole;
(polyoxyalkylene)oxazolidines;
1-(dialkylaminomethyl)-5-carboxyalkylbenzotriazole;
1-(2-hydroxyethyl)imidazoline; 1-acetoxyimidazole;
1-acetylimidazole; benzotriazolecarboxylic acid;
poly(oxyalkylated)pyrazoles; poly(oxyalkylated)thiadiazoles;
1,2,4-triazole-3-carboxylic acid; 5-hydroxypyrazole;
3-phenyl-1,2,4-triazol-5-one (ptr); 1-acetylbenzimidazole;
1-[(acetoxy)ethyl]benzimidazole; creatinine; indole-2-carboxylic
acid; pyrrole-2-carboxylic acid; imidazole-2-carboxylic acid;
pyrazole-2-carboxylic acid; and 1,1'-oxalyldimdazole. N--O Valence
Stabilizer #44: Examples of six-membered heterocyclic rings
containing one, two, three, or four nitrogen atoms at least one
additional oxygen atom binding site not in a ring (N--O Bidentates,
N--O Tridentates, N--O Tetradentates, or N--O Hexadentates) that
meet the requirements for use as "wide band" valence stabilizers
for Co.sup.+3 include, but are not limited to:
4-aminomethyl-3-pyridinemethanol (including pyridoxamine);
2-hydroxypyridine; 2-(methylhydroxy)methylpyridine;
2-(2-(methylhydroxy)ethyl)pyridine; 2,6-(hydroxymethyl)pyridine;
2,6-(methylhydroxymethyl)pyridine; 2-hydroxypyrimidine;
2-dihydroxymethylpyrimidine; 2-hydroxyquinoline; 8-hydroxyquinoline
(oxine); 8-methylhydroxyquinoline; 2-hydroxyquinazoline; orotic
acid (1,2,3,6-tetrahydro-2,6-dioxo-4-pyrimidinecarboxylic acid)
(6-uracilcarboxylic acid); 1-methylpyrimidine-2-one; uracil;
6-hydroxypurine;
bis(N,N,N',N'-tetra(2-(2-pyridyl)ethane)aminomethane)ether;
bis(N,N,N',N'-tetra(2-(2-pyridyl)ethane)aminoethane)ether;
quinazol-4-one; quinazol-2-one; 5-azathymine;
2-hydroxybenzimidazole (2-hbz); guanine; 1,3,5-triazin-6-one;
6-hydroxy-1,3,5-triazine; 4,6-dibydroxy-1,3,5-triazine; triazine
carboxylic acids; 2,3-dihydroxypyridine; thiomorpholin-3-one;
hydroxytetrahydropyrimidines; 2-piperazinones; 2-piperidinones;
dilituric acid; actinoquinol; caffeine; citrazinic acid; picolinic
acid; 2-quinolol; 2,6-dimethoxypyridine; quinoxaline-2-carboxylic
acid; flucytosine; hypoxanthine; hexamethylolmelamine; hydroorotic
acid; isoorotic acid; xanthine; leucopterin; nitroorotic acid;
8-azaguanine; and cyanuric acid. N--O Valence Stabilizer #45:
Examples of five-membered heterocyclic rings containing one or two
oxygen atoms at least one additional nitrogen atom binding site not
in a ring (N--O Bidentates, N--O Tridentates, N--O Tetradentates,
or N--O Hexadentates) that meet the requirements for use as "wide
band" valence stabilizers for Co.sup.+3 include, but are not
limited to: 2-aminofuran; 2,5-diaminofuran; 2-aminomethylfuran;
2,5-di(aminomethyl)furan; 2-aminobenzofuran; and
2-amino-1,3-dioxolane. N--O Valence Stabilizer #46: Examples of
six-membered heterocyclic rings containing one or two oxygen atoms
at least one additional nitrogen atom binding site not in a ring
(N--O Bidentates, N--O Tridentates, N--O Tetradentates, or N--O
Hexadentates) that meet the requirements for use as "wide band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
2-aminopyran; 2,6-diaminopyran; 2-aminomethylpyran;
2,6-di(aminomethyl)pyran; and 2-aminobenzopyran. N--O Valence
Stabilizer #47: Examples of five-membered heterocyclic rings
containing one, two, three, or four nitrogen atoms at least one
additional oxygen atom binding site in a separate ring (N--O
Bidentates, N--O Tridentates, N--O Tetradentates) that meet the
requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to: 2-(2-furan)pyrrole;
2,5-di(2-furan)pyrrole; 2-(2-pyran)pyrrole; 2,5-di(2-pyran)pyrrole;
2,5-di(2-pyrrole)furan; and 2,6-di(2-pyrrole)pyran. N--O Valence
Stabilizer #48: Examples of six-membered heterocyclic rings
containing one, two, three, or four nitrogen atoms at least one
additional oxygen atom binding site in a separate ring (N--O
Bidentates, N--O Tridentates, N--O Tetradentates) that meet the
requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to: 2-(2-furan)pyridine;
2,6-di(2-furan)pyridine; 2-(2-pyran)pyridine;
2,6-di(2-pyran)pyridine; 2,5-di(2-pyridyl)furan;
2,6-di(2-pyridyl)pyran; and drometrizole. N--O Valence Stabilizer
#49: Examples of two-, three-, four-, six-, eight-, and
ten-membered macrocyclics, macrobicyclics, and macropolycyclics
(including catapinands, cryptands, cyclidenes, and sepulchrates)
wherein all binding sites are composed of nitrogen (usually amine
or imine groups) or oxygen (usually hydroxy, carboxy, or carbonyl
groups) and are not contained in component heterocyclic rings (N--O
Bidentates, N-OTridentates, N--O Tetradentates, and N--O
Hexadentates) that meet the requirements for use as "wide band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
azaoxacyclobutane ([4]aneNO); azaoxacyclopentane ([5]aneNO);
azaoxacyclohexane ([6]aneNO); azaoxacycloheptane ([7]aneNO);
azaoxacyclooctane ([8]aneNO); azaoxacyclobutene ([4]eneNO);
azaoxacyclopentene ([5]eneNO); azaoxacyclohexene ([6]eneNO);
azaoxacycloheptene ([7]eneNO); azaoxacyclooctene ([8]eneNO);
azaoxacyclobutadiene ([4]dieneNO); azaoxacyclopentadiene
([5]dieneNO); azaoxacyclohexadiene ([6]dieneNO);
azaoxacycloheptadiene ([7]dieneNO); azaoxacyclooctadiene
([8]dieneNO); diazaoxacyclohexane ([6]aneON.sub.2);
diazaoxacycloheptane ([7]aneON.sub.2); diazaoxacyclooctane
([8]aneON.sub.2); diazaoxacyclononane ([9]aneON.sub.2);
diazaoxacyclodecane ([10]aneON.sub.2); diazaoxacycloundecane
([11]aneON.sub.2); diazaoxacyclododecane ([12]aneON.sub.2);
diazaoxacyclohexene ([6]eneON.sub.2); diazaoxacycloheptene
([7]eneON.sub.2); diazaoxacyclooctene ([8]eneON.sub.2);
diazaoxacyclononene ([9]eneON.sub.2); diazaoxacyclodecene
([10]eneON.sub.2); diazaoxacycloundecene ([11]eneON.sub.2);
diazaoxacyclododecene ([12]eneON.sub.2); diazadioxacyclooctane
([8]aneO.sub.2N.sub.2); diazadioxacyclononane
([9]aneO.sub.2N.sub.2); diazadioxacyclodecane
([10]aneO.sub.2N.sub.2); diazadioxacycloundecane
([11]aneO.sub.2N.sub.2); diazadioxacyclododecane
([12]aneO.sub.2N.sub.2); diazadioxacyclotridecane
([13]aneO.sub.2N.sub.2); diazadioxacyclotetradecane
([14]aneO.sub.2N.sub.2); diazadioxacyclopentadecane
([15]aneO.sub.2N.sub.2); diazadioxacyclohexadecane
([16]aneO.sub.2N.sub.2); diazadioxacycloheptadecane
([17]aneO.sub.2N.sub.2); diazadioxacyclooctadecane
([18]aneO.sub.2N.sub.2); diazadioxacyclononadecane
([19]aneO.sub.2N.sub.2); diazadioxacyclocicosane
([20]aneO.sub.2N.sub.2); diazadioxacyclooctadiene
([8]dieneo.sub.2N.sub.2); diazadioxacyclononadiene
([9]dieneo.sub.2N.sub.2); diazadioxacyclodecadiene
([10]dieneo.sub.2N.sub.2); diazadioxacycloundecadiene
([11]dieneo.sub.2N.sub.2); diazadioxacyclododecadiene
([12]dieneo.sub.2N.sub.2); diazadioxacyclotridecadiene
([13]dieneo.sub.2N.sub.2); diazadioxacyclotetradecadiene
([14]dieneO.sub.2N.sub.2); diazadioxacyclopentadecadiene
([15]dieneo.sub.2N.sub.2); diazadioxacyclohexadecadiene
([16]dieneO.sub.2N.sub.2); diazadioxacycloheptadecadiene
([17]dieneO.sub.2N.sub.2); diazadioxacyclooctadecadiene
([18]dieneo.sub.2N.sub.2); diazadioxacyclononadecadiene
([19]dieneo.sub.2N.sub.2); and diazadioxacycloeicosadiene
([20]dieneO.sub.2N.sub.2). N--O Valence Stabilizer #50: Examples of
four-, six-, eight-, or ten-membered macrocyclics, macrobicyclics,
and macropolycyclics (including catapinands, cryptands, cyclidenes,
and sepulchrates) wherein all binding sites are composed of
nitrogen or oxygen and are contained in component heterocyclic
rings (N--O Bidentates, N--O Tridentates, N--O Tetradentates, or
N--O Hexadentates) that meet the requirements for use as "wide
band" valence stabilizers for Co.sup.+3 include, but are not
limited to: dipyrandipyridines; difurandipyrroles;
tripyrantripyridines; trifurantripyrroles;
tetrapyrantetrapyridines; and tetrafurantetrapyrroles. N--O Valence
Stabilizer #51: Examples of four-, six-, eight-, or ten-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
binding sites are composed of nitrogen or oxygen and are contained
in a combination of heterocyclic rings and amine, imine, hydroxy,
carboxy, or carbonyl groups (N--O Bidentates, N--O Tridentates,
N--O Tetradentates, or N--O Hexadentates) that meet the
requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to: azaoxatetraphyrins;
diazadioxatetraphyrins; azaoxahexaphyrins; diazadioxahexaphyrins;
and triazatrioxahexaphyrins. S--O Valence Stabilizer #1: Examples
of 1,3-monothioketones (monothio-beta-ketonates),
1,3,5-monothioketones, 1,3,5-dithioketones,
bis(1,3-monothioketones), and poly(1,3-monothioketones) (S--O
Bidentates, S--O Tridentates, S--O Tetradentates) that meet the
requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to:
hexafluoropenta-2-thione-4-ketone;
1,3-diphenyl-1,3-propana-1-thione-3-ketone; benzoylthiopinacolone;
cyclohexoylthiocyclohexoylmethane; diphenylpentanedithionate;
tetramethylnonanedithionate; hexafluoroheptanedithionate;
trifluoroheptanedithionate; 1-(2-thienyl)-butan-1-thione-3-ketone,
1-(2-naphthyl)-butan-1-thione-3-ketone, and
trifluoroacetylthiocamphor. S--O Valence Stabilizer #2: Examples of
thiomalonamides (thiomalonodiamides), bis(thiomalonamides), and
polythiomalonamides (S--O Bidentates, S--O Tridentates, S--O
Tetradentates) that meet the requirements for use as "wide band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
thiomalonamide, N-phenylthiomalonamide, N-benzylthiomalonamide,
N-pentafluorophenylthiomalonamide, N-cyclohexylthiomalonamide,
N-norbornylthiomalonamide, N,N'-diphenylthiomalonamide,
N,N'-dibenzylthiomalonamide,
N,N'-dipentafluorophenylthiomalonamide,
N,N'-dicyclohexylthiomalonamide, and N,N'-norbornylthiomalonamide.
S--O Valence Stabilizer #3: Examples of 2-thioacylacetamides,
2-acylthioacetamides, bis(2-thioacylacetamides),
bis(2acylthioacetamides), poly(2-thioacylacetamides), and
poly(2-Acylthioacetamides) (S--O Bidentates, S--O Tridentates, S--O
Tetradentates) that meet the requirements for use as "wide band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
2-acetothioacetamide, 2-thioacetoacetamide,
N-phenyl-2-acetothioacetamide,
N-pentafluorophenyl-2-acetothioacetamide,
N-benzyl-2-acetothioacetamide, N-cyclohexyl-2-acetothioacetamide,
N-norbornyl-2-acetothioacetamide, N-phenyl-2-benzothioacetamide,
N-pentafluorophenyl-2-pentafluorobenzothioacetamide, and
N-cyclohexyl-2-cyclohexothioacetamide. S--O Valence Stabilizer#4:
Examples of dithiodicarbonic diamides, bis(dithiodicarbonic
diamides), and poly(dithiodicarbonic diamides) (S--O Bidentates,
S--O Tridentates, S--O Tetradentates) that meet the requirements
for use as "wide band" valence stabilizers for Co.sup.+3 include,
but are not limited to: dithiodicarbonic diamide;
N-phenyldithiodicarbonic diamide;
N-pentafluorophenyldithiodicarbonic diamide;
N-benzyldithiodicarbonic diamide; N-cyclohexyldithiodicarbonic
diamide; N-norbornyldithiodicarbonic diamide;
N,N'-diphenyldithiodicarbonic diamide;
N,N'-dipentafluorophenyldithiodicarbonic diamide;
N,N'-dibenzyldithiodicarbonic diamide;
N,N'-dicyclohexyldithiodicarbonic diamide; and
N,N'-dinorbornyldithiodicarbonic diamide. S--O Valence Stabilizer
#5: Examples of monothiohypophosphoric acids,
bis(monothiohypophosphoric acids), poly(monothiohypophosphoric
acids), and derivatives thereof (S--O Bidentates, S--O Tridentates,
S--O Tetradentates) that meet the requirements for use as "wide
band" valence stabilizers for Co.sup.+3 include, but are not
limited to: monothiohypophosphoric acid,
methylmonothiohypophosphoric acid, isopropylmonothiohypophosphoric
acid, tert-butylmonothiohypophosphoric acid,
phenylmonothiohypophosphoric acid,
pentafluorophenylmonothiohypophosphoric acid,
benzylmonothiohypophosphoric acid, cyclohexylmonothiohypophosphoric
acid, norbornylmonothiohypophosphoric acid,
dimethylmonothiohypophosphoric acid,
diisopropylmonothiohypophosphoric acid,
di-tert-butylmonothiohypophosphoric acid,
diphenylmonothiohypophosphoric acid,
di-pentafluorophenylmonothiohypophosphoric acid,
dibenzylmonothiohypophosphoric acid,
dicyclohexylmonothiohypophosphoric acid, and
dinorbornylmonothiohypophosphoric acid. S--O Valence Stabilizer #6:
Examples of monothiohypophosphoramides,
bis(monothiohypophosphoramides), and
poly(monothiohypophosphoramides) (S--O Bidentates, S--O
Tridentates, S--O Tetradentates) that meet the requirements for use
as "wide band" valence slabilizers for Co.sup.3 include, but are
not limited to: monothiohypophosphoramide,
N-methylmonothiohypophosphoramide,
N-isopropylmonothiohypophosphoramide,
N-tert-butylmonothiobypophosphoramide,
N-phenylmonothiohypophosphoramide,
N-pentafluorophenylmonothiohypophosphoramide,
N-benzylmonothiohypophosphoramide,
N-cyclohexylmonothiohypophosphoramide,
N-norbornylmonothiohypophosphoramide,
N,N'''-dimethylmonothiohypophosphoramide,
N,N'''-diisopropylmonothiohypophosphoramide,
N,N'''-di-tert-butylmonothiohypophosphoramide,
N,N'''-diphenylmonothiohypophosphoramide,
N,N'''-di-pentafluorophenylmonothiohypophosphoramide,
N,N'''-dibenzylmonothiohypophosphoramide,
N,N'''-dicyclohexylmonothiohypophosphoramide, and
N,N'''-dinorbornylmonothiohypophosphoramide. S--O Valence
Stabilizer #7: Examples of monothioimidodiphosphoric acids,
monothiohydrazidodiphosphoric acids, bis(monothioimidodiphosphoric
acids), bis(monothiohydrazidodiphosphoric acids),
poly(monothioimidodiphosphoric acids),
poly(monothiohydrazidodiphosphoric acids), and derivatives thereof
(S--O Bidentates, S--O Tridentates, S--O Tetradentates) that meet
the requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to:
monothioimidodiphosphoric acid, methylmonothioimidodiphosphoric
acid, isopropylmonothioimidodiphosphoric acid,
tert-butylmonothioimidodiphosphoric acid,
phenylmonothioimidodiphosphoric acid,
pentafluorophenylmonothioimidodiphosphoric acid,
benzylmonothioimidodiphosphoric acid,
cyclohexylmonothioimidodiphosphoric acid,
norbornylmonothioimidodiphosphoric acid,
dimethylmonothioimidodiphosphoric acid,
diisopropylmonothioimidodiphosphoric acid,
di-tert-butylmonothioimidodiphosphoric acid,
diphenylmonothioimidodiphosphoric acid,
di-pentafluorophenylmonothioimidodipbosphoric acid,
dibenzylmonothioimidodiphosphoric acid,
dicyclohexylmonothioimidodiphosphoric acid, and
dinorbornylmonothioimidodiphosphoric acid. S--O Valence Stabilizer
#8: Examples of monothioimidodiphosphoramides,
monothiohydrazidodiphosphoramides,
bis(monothioimidodiphosphoramides),
bis(monothiohydrazidodiphosphoramides),
poly(monothioimidodiphosphoramides), and
poly(monothiohydrazidodiphosphoramides) (S--O Bidentates, S--O
Tridentates, S--O Tetradentates) that meet the requirements for use
as "wide band" valence stabilizers for Co.sup.+3 include, but are
not limited to: monothioimidodiphosphoramide,
N-methylmonothioimidodiphosphoramide,
N-isopropylmonothioimidodiphosphoramide,
N-tert-butylmonothioimidodiphosphoramide,
N-phenylmonothioimidodiphosphoramide,
N-pentafluorophenylmonothioimidodiphosphoramide,
N-benzylmonothioimidodiphosphoramide,
N-cyclohexylmonothioimidodiphosphoramide,
N-norbornylmonothioimidodiphosphoramide,
N,N'''-dimethylmonothioimidodiphosphoramide,
N,N'''-diisopropylmonothioimidodiphosphoramide,
N,N'''-di-tert-butylmonothioimidodiphosphoramide,
N,N'''-diphenylmonothioimidodiphosphoramide,
N,N'''-di-pentafluorophenylmonothioimidodiphosphoramide,
N,N'''-dibenzylmonothioimidodiphosphoramide,
N,N'''-dicyclohexylmonothioimidodiphosphoramide, and
N,N'''-dinorbornylmonothioimidodiphosphoramide. S--O Valence
Stabilizer #9: Examples of monothiodiphosphoramides,
bis(monothiodiphosphoramides), and poly(monothiodiphosphoramides)
(S--O Bidentates, S--O Tridentates, S--O Tetradentates) that meet
the requirements for use as "wide band" valence stabilizers for
Co.sup.+3 include, but are not limited to: monothiodiphosphoramide,
N-methylmonothiodiphosphoramide,
N-isopropylmonothiodiphosphoramide,
N-tert-butylmonothiodiphosphoramide,
N-phenylmonothiodiphosphoramide,
N-pentafluorophenylmonothiodiphosphoramide,
N-benzylmonothiodiphosphoramide,
N-cyclohexylmonothiodiphosphoramide,
N-norbornylmonothiodiphosphoramide,
N,N'''-dimethylmonothiodiphosphoramide,
N,N'''-diisopropylmonothiodiphosphoramide,
N,N'''-di-tert-butylmonothiodiphosphoramide,
N,N'''-diphenylmonothiodiphosphoramide,
N,N'''-di-pentafluorophenylmonothiodiphosphoramide,
N,N'''-dibenzylmonothiodiphosphoramide,
N,N'''-dicyclohexylmonothiodiphosphoramide, and
N,N'''-dinorbornylmonothiodiphosphoramide. S--O Valence
Stabilizer#10: Examples of monothiodiphosphoric acids,
bis(monothiodiphosphoric acids), poly(monothiodiphosphoric acids),
and derivatives thereof (S--O Bidentates, S--O Tridentates, S--O
Tetradentates) that meet the requirements for use as "wide band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
monothiodiphosphoric acid, methylmonothiodiphosphoric acid,
isopropylmonothiodiphosphoric acid, tert-butylmonothiodiphosphoric
acid, phenylmonothiodiphosphoric acid,
pentafluorophenylmonothiodiphosphoric acid,
benzylmonothiodiphosphoric acid, cyclohexylmonothiodiphosphoric
acid, norbornylmonothiodiphosphoric acid,
dimethylmonothiodiphosphoric acid, diisopropylmonothiodiphosphoric
acid, di-tert-butylmonothiodiphosphoric acid,
diphenylmonotbiodiphosphoric acid,
di-pentafluorophenylmonothiodiphosphoric acid,
dibenzylmonothiodiphosphoric acid, dicyclohexylmonothiodiphosphoric
acid, and dinorbornylmonothiodiphosphoric acid. S--O Valence
Stabilizer #11: Examples of monothiocarbamates,
bis(monothiocarbamates), and poly(monothiocarbamates) (including
N-hydroxymonothiocarbamates and N-mercaptomonothiocarbamates) (S--O
Bidentates, S--O Tridentates, and S--O Tetradentates) that meet the
requirements for use as "wide band" valence stabilizers for Co
.sup.3 include, but are not limited to: dimethylmonothiocarbamate
(dmmtc); di(trifluorodimethyl)monothiocarbamate;
diethylmonothiocarbamate (demtc); dipropylmonothiocarbamate;
diisopropylmonothiocarbamate; dibutylmonothiocarbamate;
ditertbutylmonothiocarbamate; dicyanamidomonothiocarbamate;
diphenylmonothiocarbamate; di(pentafluorophenyl)monothiocarbamate;
dibenzylmonothiocarbamate; dinaphthylmonothiocarbamate;
dicyclohexylmonothiocarbamate; dinorbornylmonothiocarbamate;
diadamantylmonothiocarbamate; pyrrolidinomonothiocarbamate
(pyrmtc); piperidinomonothiocarbamate (pipmtc);
morpholinomonothiocarbamate (mormtc);
thiamorpholinomonothiocarbamate; 3-pyrrolinomonothiocarbamate;
pyrrolomonothiocarbamate; oxazolomonothiocarbamate;
isoxazolomonothiocarbamate; thiazolomonothiocarbamate;
isothiazolomonothiocarbamate; indolomonothiocarbamate;
carbazolomonothiocarbamate; pyrazolinomonothiocarbamate;
imidazolinomonothiocarbamate; pyrazolomonothiocarbamate;
imidazolomonothiocarbamate; indazolomonothiocarbamate; and
triazolomonothiocarbamate.
Water-soluble precursors for the organic valence stabilizers are
typically used to ensure that sufficient material is available for
coating deposition from aqueous solutions. Identification of
suitable water soluble precursors can be difficult because many of
these organics do not form a wide range of water-soluble
compounds.
As with the inorganic valence stabilizers, crosses between two or
more organic valence stabilizers can be used to stabilize Co.sup.+3
for corrosion protection. For example, in some instances it may be
desirable to form a valence stabilizer out of a nitrogen-containing
heterocyclic and an amine ligand. Both of these materials can
complex to form a mixed nitrogen heterocyclic/amine valence
stabilizer out of the conversion coating solution during the
coating process.
4c) Narrow Band Inorganic Valence Stabilizers
Narrow band valence stabilizers can be used to stabilize Co.sup.+3
for corrosion protection, but they are less typical. Narrow band
valence stabilizers exhibit some limitation in their use when
compared to wide band stabilizers. They may be toxic or may complex
Co.sup.+3 only with difficulty. These narrow band stabilizers
include, but are not limited to, bismuthates, germanates,
arsenates, litanates, zirconates, and hafnates. For example,
valence stabilizers using arsenate are less desirable because their
inherent toxicity is very large (greater than hexavalent chromium),
although they may be very effective at inhibiting corrosion when
used with Co.sup.+3. Arsenates can be used as valence stabilizers
for Co.sup.+3 when the toxicity of the coating solution is not a
factor in its use.
Other narrow band stabilizers may result in Co.sup.+3-stabilizer
complexes with limited stability, an undesirable solubility range,
or limited electrostatic characteristics, and they would be useful
only in limited applications. Formation of a protective shell of
octahedra or tetrahedra with phosphates (P.sup.+5), borates
(B.sup.+3), aluminates (Al.sup.+3), and silicates (Si.sup.+4)
around the Co.sup.+3 ion is difficult but possible. These compounds
are known to form octahedra or tetrahedra, but tend to polymerize
in chain-like structures when precipitated from aqueous solution
under ambient conditions. These and other narrow band stabilizers
can provide some degree of corrosion protection when complexed with
Co.sup.+3, but will not necessarily perform with the same
efficiency as the wide band stabilizers by themselves. Combinations
of these materials, such as phosphosilicates, aluminosilicates, or
borosilicates may also function as narrow band inorganic valence
stabilizers.
Narrow band inorganic stabilizers used in combination with wide
band inorganic stabilizers described above can be used to provide
significant corrosion protection. Conversely, modifications of wide
band inorganic valence stabilizers can result in a complex with
reduced corrosion inhibition. For example, heteropolymetallates can
contain ions in addition to the desired Co.sup.+3 ion.
The central cavity of the heteropolymetallates can contain ions in
addition to the desired Co.sup.+3 ion. For example, the use of
silicomolybdates, phosphomolybdates, silicotungstates, and
phosphotungstates is possible. In these Co.sup.+3-valence
stabilizer complexes, Si.sup.+4 or p.sup.+5 ions also occupy the
central cavity of the complex with the Co.sup.+3 ion. The inclusion
of additional ions in the central cavity reduces the stability of
the complex, and thereby leads to lower corrosion protection.
Nonetheless, these complexes also demonstrated some corrosion
inhibiting activity.
The additional ions that can be included within the central cavity
of the heteropolymetallates described above depend upon the size of
the central cavity, which in turn depends upon the specific
chemistry exhibited by an inorganic valence stabilizer (e.g.,
molybdate, tungstate, periodate, carbonate, etc.). In general,
these additional ions must also be small so as to ensure the
stability of the formed Co.sup.+3-valence stabilized complex.
Examples of small additional ions include, but are not limited to:
B.sup.+3, Al.sup.+3, Si.sup.+4, p.sup.+5, Ti.sup.+4, V.sup.+5,
V.sup.+4, Cr.sup.+6, Cr.sup.+4, Cr.sup.+3, Mn.sup.+4, Mn.sup.+3,
Mn.sup.+2, Fe.sup.+3, Fe.sup.+2, Co.sup.+2 Ni.sup.+2 Ni.sup.+4,
Cu.sup.+2, Cu.sup.+3, Zn.sup.+2, Ga.sup.+3, Ge.sup.+4, As,
As.sup.+3, Zr, and Ce.sup.+4.
Water-soluble precursors for these materials are desirable.
Typically, the free acids (e.g., silicomolybdic acid,
phosphotungstic acid, borotungstic acid, etc.) offer the most
water-soluble precursors for these materials.
4d) Narrow Band Organic Valence Stabilizers
Narrow band organic valence stabilizers include those general
classes of chemical compounds that result in Co.sup.+3-valence
stabilizer complexes that are either less stable, more soluble in
water, or more toxic than the wide band organic stabilizers.
TABLE-US-00003 TABLE 2 Narrow Band Organic Valence Stabilizers for
the Co.sup.+3 Ion General Structural Name (Type of Organic)
Structural Representation N Valence Stabilizer #1: Macrocyclic
ligands containing five, seven, or Five-, Seven-, or Nine-Membered
nine nitrogen binding sites to valence stabilize Macrocyclics,
Macrobicyclics, and the central metal ion. Can include other
Macropolycyclics (including Catapinands, hydrocarbon or ring
systems bound to this Cryptands, Cyclidenes, and Sepulchrates)
macrocyclic ligand, but they do not coordinate wherein all Binding
Sites are composed of with the stabilized, high valence metal ion.
Nitrogen (usually amine or imine groups) This ligand and/or
attached, uncoordinating and are not contained in Component
hydrocarbons/rings may or may not have Heterocyclic Rings (N--N
Tridentates, N--N halogen or polarizing or water- Tetradentates,
and N--N Hexadentates) insolubilizing/solubilizing groups attached.
N Valence Stabilizer #2: Macrocyclic ligands containing a total of
five or Five-, or Seven-Membered Macrocyclics, seven five-membered
heterocyclic rings Macrobicyclics, and Macropolycyclics containing
nitrogen binding sites. Can include (including Catapinands,
Cryptands, other hydrocarbon/ring systems bound to this Cyclidenes,
and Sepulchrates) wherein all macrocyclic ligand, but they do not
coordinate Binding Sites are composed of Nitrogen with the
stabilized, high valence metal ion. and are contained in Component
5- This ligand and/or attached, uncoordinating Membered
Heterocyclic Rings (N--N hydrocarbon/rings may or may not have
Tridentates, N--N Tetradentates, or N--N halogen or polarizing or
water-insolubilizing Hexadentates) groups attached. N Valence
Stabilizer #3: Macrocyclic ligands containing at least one 5-
Five-, Seven-, or Nine-Membered membered heterocyclic ring. These
Macrocyclics, Macrobicyclics, and heterocyclic rings provide
nitrogen binding sites Macropolycyclics (including Catapinands, to
valence stabilize the central metal ion. Other Cryptands,
Cyclidenes, and Sepulchrates) amine or imine binding sites can also
be wherein all Binding Sites are composed of included in the
macrocyclic ligand, so long as Nitrogen and are contained in a the
total number of binding sites is five, seven, Combination of
5-Membered Heterocyclic or nine. Can include other hydrocarbon/ring
Rings and Amine or Imine Groups (N--N systems bound to this
macrocyclic ligand, but Tridentates, N--N Tetradentates, or N--N
they do not coordinate with the stabilized, high Hexadentates)
valence metal ion. This ligand and/or attached, uncoordinating
hydrocarbon/rings may or may not have halogen or polarizing or
water- insolubilizing groups attached. N Valence Stabilizer #4:
Macrocyclic ligands containing a total of five or Five- or
Seven-Membered Macrocyclics, seven six-membered heterocyclic rings
Macrobicyclics, and Macropolycyclics containing nitrogen binding
sites. Can include (including Catapinands, Cryptands, other
hydrocarbon/ring systems bound to this Cyclidenes, and
Sepulchrates) wherein all macrocyclic ligand, but they do not
coordinate Binding Sites are composed of Nitrogen with the
stabilized, high valence metal ion. and are contained in Component
6- This ligand and/or attached, uncoordinating Membered
Heterocyclic Rings (N--N hydrocarbon/rings may or may not have
Tridentates, N--N Tetradentates, or N--N halogen or polarizing or
water-insolubilizing Hexadentates) groups attached. N Valence
Stabilizer #5: Macrocyclic ligands containing at least one 6-
Five-, Seven-, or Nine-Membered membered heterocyclic ring. These
Macrocyclics, Macrobicyclics, and heterocyclic rings provide
nitrogen binding sites Macropolycyclics (including Catapinands, to
valence stabilize the central metal ion. Other Cryptands,
Cyclidenes, and Sepulchrates) amine or imine binding sites can also
be wherein all Binding Sites are composed of included in the
macrocyclic ligand, so long as Nitrogen and are contained in a the
total number of binding sites is five, seven, Combination of
6-Membered Heterocyclic or nine. Can include other hydrocarbon/ring
Rings and Amine or Imine Groups (N--N systems bound to this
macrocyclic ligand, but Tridentates, N--N Tetradentates, or N--N
they do not coordinate with the stabilized, high Hexadentates)
valence metal ion. This ligand and/or attached, uncoordinating
hydrocarbon/rings may or may not have halogen or polarizing or
water- insolubilizing groups attached. N Valence Stabilizer #6:
N(SiR.sub.3).sub.3, R'N(SiR.sub.3).sub.2, or R'R''N(SiR.sub.3) for
Silylamines and Silazanes, including silylamines; and
[RR''Si--NR'].sub.x (x = 1-10) for Macrocyclic Derivatives, wherein
at least silazanes where R, R', and R'' represents H or one
Nitrogen Atom is a Binding Site (N any organic functional group
wherein the Monodentates, N--N Bidentates, N--N number of carbon
atoms ranges from 0 to 35, Tridentates, N--N Tetradentates, and
N--N optionally having halogen or polarizing or Hexadentates)
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, P, As, O, S, or Se atoms. N Valence
Stabilizer #7: RR'--N--C(.dbd.NH)NR''R''', where R, R', R'', and
Guanidines, Diguanidines, and R''' represent H or any organic
functional group Polyguanidines (N--N Bidentates, N--N wherein the
number of carbon atoms ranges Tridentates, N--N Tetradentates, and
N--N from 0 to 40, optionally having halogen or Hexadentates)
polarizing or water-insolubilizing/solubilizing groups attached.
Ligand can also contain nonbinding N, O, S, or P atoms. N Valence
Stabilizer #8: RR'--N--P(.dbd.N)--N--R''R''', where R, R', R'', and
Phosphonitrile Amides, and R''' represent H or any organic
functional group Bis(phosphonitrile amides) (N--N wherein the
number of carbon atoms ranges Bidentates, N--N Tetradentates) from
0 to 40, optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N Valence Stabilizer #9:
(NH.dbd.)PR'''(--NRR')(--NR''R'''), where R, R', Phosphonimidic
Diamides, R'', R''', and R'''' represent H or any organic
Bis(Phosphonimidic Diamides), and functional group wherein the
number of carbon Poly(Phosphonimidic Diamides) (N--N atoms ranges
from 0 to 40, optionally having Bidentates, N--N Tetradentates)
halogen or polarizing or water- insolubilizing/solubilizing groups
attached. Ligand can also contain nonbinding N, O, S, or P atoms. N
Valence Stabilizer #10: (NH.dbd.)PR'''(--NRR')(--OR'') for
Phosphonamidimidic Acid, phosphonamidimidic acid and (NH.dbd.)PR'''
Phosphonamidimidothioic Acid, (--NRR')(--SR'') for
phosphonamidimidothioic Bis(Phosphonamidimidic Acid), acid, where
R, R', R'', and R''' represent H or Bis(Phosphonamidimidothioic
Acid), any organic functional group wherein the
Poly(Phosphonamidimidic Acid), number of carbon atoms ranges from 0
to 40, Poly(Phosphonamidimidothioic Acid), and optionally having
halogen or polarizing or derivatives thereof (N--N Bidentates, and
water-insolubilizing/solubilizing groups N--N Tetradentates)
attached. Ligand can also contain nonbinding N, O, S, or P atoms. N
Valence Stabilizer #11: C.sub.5H.sub.5N--CR--NR', where
C.sub.5H.sub.5N is a pyridine Pyridinaldimines,
Bis(pyridinaldimines), derivative, R is typically an aromatic and
Poly(pyridinaldimines) (N--N constituent (i.e. --C.sub.6H.sub.5),
and R' represents H or Bidentates, N--N Tridentates, and N--N any
organic functional group wherein the Tetradentates) number of
carbon atoms ranges from 0 to 40, optionally having halogen or
polarizing or water-insolubilizing/solubilizing groups attached.
Ligand can also contain nonbinding N, O, S, or P atoms. N Valence
Stabilizer #12: R--NH--N.dbd.R', where R and R' represent H or
Hydrazones, Bis(hydrazones), and any organic functional group
wherein the Poly(hydrazones) (N Monodentates, N--N number of carbon
atoms ranges from 0 to 40, Bidentates, N--N Tridentates, and N--N
optionally having halogen or polarizing or Tetradentates)
water-insolubilizing/solubilizing groups attached. (Either R or R'
is typically an aryl group.) Ligand can also contain nonbinding N,
O, S, or P atoms. N Valence Stabilizer #13: R--N.dbd.N--R' for azo
compounds, R--N.dbd.N--NH--R' Azo compounds including triazenes for
triazenes, where R, and R' represent H or without chelate
substitution at the ortho- any organic functional group wherein the
(for aryl) or alpha- or beta- (for alkyl) number of carbon atoms
ranges from 0 to 40, positions, Bis(azo compounds), or Poly(azo
optionally having halogen or polarizing or compounds) (N
Monodentates, N--N water-insolubilizing/solubilizing groups
Bidentates, or N--N--N Tridentates) attached. (Not including ortho-
chelate substituted aryl azo compounds, and alpha- or
beta-substituted alkyl azo compounds.) Ligand can also contain
nonbinding N, O, S, or P atoms. N Valence Stabilizer #14:
R--N.dbd.N--CR'N--NR''R''', where R, R', R'', and Formazans,
Bis(formazans), and R''' represent H, or any organic functional
Poly(formazans) without ortho- hydroxy, group wherein the number of
carbon atoms carboxy, thiol, mercapto, amino, or ranges from 0 to
40, optionally having halogen hydrazido substitution (N--N
Bidentates, or polarizing or water- N--N Tetradentates, and N--N
Hexadentates) insolubilizing/solubilizing groups attached. (Not
including ortho- hydroxy, carboxy, thiol, mercapto, amino, or
hydrazido substitution.) Ligand can also contain nonbinding N, O,
S, or P atoms. N Valence Stabilizer #15:
R--CH.dbd.N--CHR'--N.dbd.CHR'', where R, R', and R'' Hydramides
(N--N Bidentates) represent H, or any organic functional group
wherein the number of carbon atoms ranges from 0 to 40, optionally
having halogen or polarizing or water-insolubilizing/solubilizing
groups attached. (R, R', and R'' are typically aryl derivatives.)
Ligand can also contain nonbinding N, O, S, or P atoms. N Valence
Stabilizer #16: RR'C.dbd.N--N.dbd.CR''R''' or RR'C.dbd.N--NR''R'''
(for Azines (including ketazines), Bis(azines), ketazines), where
R, R', R'', and R''' represent and Poly(azines) without ortho-
hydroxy, H, or any organic functional group wherein the carboxy,
thiol, mercapto, amino, or number of carbon atoms ranges from 0 to
40, hydrazido substitution (N--N Bidentates, optionally having
halogen or polarizing or N--N Tetradentates, and N--N Hexadentates)
water-insolubilizing/solubilizing groups attached. (Not including
ortho- hydroxy, carboxy, thiol, mercapto, amino, or hydrazido
substitution.) Ligand can also contain nonbinding N, O, S, or P
atoms. N Valence Stabilizer #17: RR'C.dbd.N--R'', where R, R', and
R'' represent H, Schiff Bases with one Imine (C.dbd.N) Group or any
organic functional
group wherein the and without ortho- (for aryl constituents) or
number of carbon atoms ranges from 0 to 40, alpha- or beta- (for
alkyl constituents) optionally having halogen or polarizing or
hydroxy, carboxy, carbonyl, thiol,
water-insolubilizing/solubilizing groups mercapto, thiocarbonyl,
amino, imino, attached. (Not including ortho-, alpha-, or beta-
oximo, diazeno, or hydrazido substitution hydroxy, carboxy,
carbonyl, thiol, mercapto, (N Monodentates) thiocarbonyl, amino,
imino, oximo, diazeno, or hydrazido substitution.) Ligand can also
contain nonbinding N, O, S, or P atoms. N Valence Stabilizer #18:
Isocyanides, cyanamides, and related ligands Isocyanide and
Cyanamide and related where the nitrogen atom is directly complexed
ligands (N Monodentates) to the high valence metal ion. N Valence
Stabilizer #19: Nitrosyl, nitrite, and related ligands where the
Nitrosyl and Nitrite and related ligands (N nitrogen atom is bound
directly to the high Monodentates) valence metal ion. N Valence
Stabilizer #20: R--CN, R--(CN).sub.2, R--(CN).sub.x, etc. where R
Nitriles, Dinitriles, and Polynitriles (N represents H or any
organic functional group Monodentates, N--N Bidentates, and N--N--N
wherein the number of carbon atoms ranges Tridentates) from 0 to
40, optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. N Valence
Stabilizer #21: Azide (--N.sub.3) ligands bound directly to the
high Azide ligands (N Monodentates, or N--N valence metal ion. Also
includes organoazide Bidentates) derivatives (R--N.sub.3),
triazenido compounds (R--N.sub.3--R'), phosphonyl azides
(R--PO.sub.2H--N.sub.3), phosphoryl azides (O--PO.sub.2H--N.sub.3),
and sulfonyl azides (R--SO.sub.2--N.sub.3) where R and R' represent
H or any organic functional group wherein the number of carbon
atoms ranges from 0 to 35, optionally having halogen or polarizing
or water-insolubilizing/solubilizing groups attached S Valence
Stabilizer #1: SH.sub.2, SHR, SR.sub.2, where R represents H or any
Monothioethers (S Monodentates) wherein organic functional group
wherein the number of at least one Sulfur Atom is a Binding Site
carbon atoms ranges from 0 to 35, optionally having halogen or
polarizing or water- insolubilizing/solubilizing groups attached.
Ligand can also contain nonbinding N, P, O, S, or Se atoms. S
Valence Stabilizer #2: R--S--S--R', where R and R' represents H or
any Disulfides (S Monodentates) wherein at organic functional group
wherein the number of least one Sulfur Atom is a Binding Site
carbon atoms ranges from 0 to 35, optionally having halogen or
polarizing or water- insolubilizing/solubilizing groups attached.
Ligand can also contain nonbinding N, P, O, S, or Se atoms. S
Valence Stabilizer #3: R--S--R'--S--R'', where R, R', and R''
represents H Dithioethers (S--S Bidentates) wherein at or any
organic functional group wherein the least one Sulfur Atom is a
Binding Site number of carbon atoms ranges from 0 to 35, optionally
having halogen or polarizing or water-insolubilizing/solubilizing
groups attached. Ligand can also contain nonbinding N, P, O, S, or
Se atoms. S Valence Stabilizer #4: R--S--R'--S--R''--S--R''', where
R, R', R'', and R''' Trithioethers (S--S Bidentates or S--S
represents H or any organic functional group Tridentates) wherein
at least one Sulfur wherein the number of carbon atoms ranges Atom
is a Binding Site from 0 to 35, optionally having halogen or
polarizing or water-insolubilizing/solubilizing groups attached.
Ligand can also contain nonbinding N, P, O, S, or Se atoms. S
Valence Stabilizer #5: R--S--R'--S--R''--S--R'''--S--R'''', where
R, R', R'', Tetrathioethers (S--S Bidentates, S--S R''', and R''''
represents H or any organic Tridentates, or S--S Bidentates)
wherein at functional group wherein the number of carbon least one
Sulfur Atom is a Binding Site atoms ranges from 0 to 35, optionally
having halogen or polarizing or water- insolubilizing/solubilizing
groups attached. Ligand can also contain nonbinding N, P, O, S, or
Se atoms. S Valence Stabilizer #6:
R--S--R'--S--R''--S--R'''--S--R''''--S--R'''''--S--R'''''',
Hexathioethers (S--S Bidentates, S--S where R, R', R'', R''',
R'''', R''''', and R'''''' Tridentates, S--S Tetradentates, or S--S
represents H or any organic functional group Hexadentates) wherein
at least one Sulfur wherein the number of carbon atoms ranges Atom
is a Binding Site from 0 to 35, optionally having halogen or
polarizing or water-insolubilizing/solubilizing groups attached.
Ligand can also contain nonbinding N, P, O, S, or Se atoms. S
Valence Stabilizer #7: Five membered heterocyclic ring containing
Five-Membered Heterocyclic Rings one or two sulfur atoms, both of
which may containing One or Two Sulfur Atoms function as binding
sites. Can include other wherein at least one Sulfur Atom is a ring
systems bound to this heterocyclic ring, but Binding Site (S
Monodentates or S--S they do not coordinate with the stabilized,
high Bidentates) valence metal ion. Ring can also contain O, N, P,
As, or Se atoms. This 5-membered ring and/or attached,
uncoordinating rings may or may not have halogen or polarizing or
water insolubilizing/solubilizing groups attached. S Valence
Stabilizer #8: Six membered heterocyclic ring containing just
Six-Membered Heterocyclic Rings one or two sulfur atoms, both of
which may containing One or Two Sulfur Atoms function as binding
sites. Can include other wherein at least one Sulfur Atom is a ring
systems bound to this heterocyclic ring, but Binding Site (S
Monodentates or S--S they do not coordinate with the stabilized,
high Bidentates) valence metal ion. Ring can also contain O, N, P,
As, or Se atoms. This 5-membered ring and/or attached,
uncoordinating rings may or may not have halogen or polarizing or
water- insolubilizing/solubilizing groups attached. S Valence
Stabilizer #9: Five membered heterocyclic ring(s) containing
Five-Membered Heterocyclic Rings one or two sulfur atoms. In
addition, ligand containing One or Two Sulfur Atoms at contains
additional sulfur-containing least one additional Sulfur Atom
Binding substituents (usually thiols or thioethers) that Site not
in a Ring (S Monodentates, S--S constitute S binding sites. Can
include other Bidentates, S--S Tridentates, S--S ring systems bound
to the heterocyclic ring or Tetradentates, or S--S Hexadentates) to
the S-containing substituent, but they do not coordinate with the
stabilized, high valence metal ion. Ring(s) can also contain O, N,
P, As or Se atoms. This 5-membered ring(s) and/or attached,
uncoordinating rings and/or S- containing substituent(s) may or may
not have halogen or polarizing or water-
insolubilizing/solubilizing groups attached. S Valence Stabilizer
#10: Six membered heterocyclic ring(s) containing Six-Membered
Heterocyclic Rings one or two sulfur atoms. In addition, ligand
containing One or Two Sulfur Atoms at contains additional
sulfur-containing least one additional Sulfur Atom Binding
substituents (usually thiols or thioethers) that Site not in a Ring
(S Monodentates, S--S constitute S binding sites. Can include other
Bidentates, S--S Tridentates, S--S ring systems bound to the
heterocyclic ring or Tetradentates, or S--S Hexadentates) to the
S-containing substituent, but they do not coordinate with the
stabilized, high valence metal ion. Ring(s) can also contain O, N,
P, As or Se atoms. This 6-membered ring(s) and/or attached,
uncoordinating rings and/or S- containing substituent(s) may or may
not have halogen or polarizing or water-
insolubilizing/solubilizing groups attached. S Valence Stabilizer
#11: Five membered heterocyclic ring(s) containing Five-Membered
Heterocyclic Rings one or two sulfur atoms. In addition, ligand
containing One or Two Sulfur Atoms at contains additional
sulfur-containing rings that least one additional Sulfur Atom
Binding constitute S binding sites. Can include other Site in a
separate Ring (S Monodentates, ring systems bound to the
S-containing S--S Bidentates, S--S Tridentates, S--S heterocyclic
rings, but they do not coordinate Tetradentates, or S--S
Hexadentates) with the stabilized, high valence metal ion. Ring(s)
can also contain O, N, P, As, or Se atoms. This 5-membered ring(s)
and/or additional S-containing ring(s) and/or attached,
uncoordinating rings may or may not have halogen or polarizing or
water- insolubilizing/solubilizing groups attached. S Valence
Stabilizer #12: Six membered heterocyclic ring(s) containing
Six-Membered Heterocyclic Rings one or two sulfur atoms. In
addition, ligand containing One or Two Sulfur Atoms at contains
additional sulfur-containing rings that least one additional Sulfur
Atom Binding constitute S binding sites. Can include other Site in
a separate Ring (S Monodentates, ring systems bound to the
S-containing S--S Bidentates, S--S Tridentates, S--S heterocyclic
rings, but they do not coordinate Tetradentates, or S--S
Hexadentates) with the stabilized, high valence metal ion. Ring(s)
can also contain O, N, P, As, or Se atoms. This 6-membered ring(s)
and/or additional S-containing ring(s) and/or attached,
uncoordinating rings may or may not have halogen or polarizing or
water- insolubilizing/solubilizing groups attached. S Valence
Stabilizer #13: Macrocyclic ligands containing two to ten Two-,
Three-, Four-, Five-, Six-, Seven-, sulfur binding sites to valence
stabilize the Eight-, Nine-, and Ten-Membered central metal ion.
Can include other Macrocyclics, Macrobicyclics, and hydrocarbon or
ring systems bound to this Macropolycyclics (including Catapinands,
macrocyclic ligand, but they do not coordinate Cryptands,
Cyclidenes, and Sepulchrates) with the stabilized, high valence
metal ion. wherein all Binding Sites are composed of This ligand
and/or attached, uncoordinating Sulfur (usually thiol or thioether
groups) hydrocarbons/rings may or may not have and are not
contained in Component halogen or polarizing or water- Heterocyclic
Rings (S--S Bidentates, S--S insolubilizing/solubilizing groups
attached. Tridentates, S--S Tetradentates, and S--S Hexadentates) S
Valence Stabilizer #14: Macrocyclic ligands containing a total of
four to Four-, Five-, Six-, Seven-, Eight-, Nine-, or ten
five-membered heterocyclic rings Ten-Membered Macrocyclics,
containing sulfur binding sites. Can include Macrobicyclics, and
Macropolycyclics other hydrocarbon/ring systems bound to this
(including Catapinands, Cryptands, macrocyclic ligand, but they do
not coordinate Cyclidenes, and Sepulchrates) wherein all with the
stabilized, high valence metal ion. Binding Sites are composed of
Sulfur and This ligand and/or attached, uncoordinating are
contained in Component 5-Membered hydrocarbon/rings may or may not
have Heterocyclic Rings (S--S Tridentates, S--S halogen or
polarizing or water-insolubilizing Tetradentates or S--S
Hexadentates) groups attached.
S Valence Stabilizer #15: Macrocyclic ligands containing at least
one 5- Four-, Five-, Six-, Seven-, Eight-, Nine-, or membered
heterocyclic ring. These Ten-Membered Macrocyclics, heterocyclic
rings provide sulfur binding sites Macrobicyclics, and
Macropolycyclics to valence stabilize the central metal ion. Other
(including Catapinands, Cryptands, thiol, thioether, or thioketo
binding sites can Cyclidenes, and Sepulchrates) wherein all also be
included in the macrocyclic ligand, so Binding Sites are composed
of Sulfur and long as the total number of binding sites is four are
contained in a Combination of 5- to ten. Can include other
hydrocarbon/ring Membered Heterocyclic Rings and Thiol, systems
bound to this macrocyclic ligand, but Thioether, or Thioketo Groups
(S--S they do not coordinate with the stabilized, high Tridentates,
S--S Tetradentates, or S--S valence metal ion. This ligand and/or
attached, Hexadentates) uncoordinating hydrocarbon/rings may or may
not have halogen or polarizing or water- insolubilizing groups
attached. S Valence Stabilizer #16: Macrocyclic ligands containing
a total of four to Four-, Five-, Six-, Seven-, Eight-, Nine-, or
ten six-membered heterocyclic rings containing Ten-Membered
Macrocyclics, sulfur binding sites. Can include other
Macrobicyclics, and Macropolycyclics hydrocarbon/ring systems bound
to this (including Catapinands, Cryptands, macrocyclic ligand, but
they do not coordinate Cyclidenes, and Sepulchrates) wherein all
with the stabilized, high valence metal ion. Binding Sites are
composed of Sulfur and This ligand and/or attached, uncoordinating
are contained in Component 6-Membered hydrocarbon/rings may or may
not have Heterocyclic Rings (S--S Tridentates, S--S halogen or
polarizing or water-insolubilizing Tetradentates, or S--S
Hexadentates) groups attached. S Valence Stabilizer #17:
Macrocyclic ligands containing at least one 6- Four-, Five-, Six-,
Seven-, Eight-, Nine-, or membered heterocyclic ring. These
Ten-Membered Macrocyclics, heterocyclic rings provide sulfur
binding sites Macrobicyclics, and Macropolycyclics to valence
stabilize the central metal ion. Other (including Catapinands,
Cryptands, thiol, thioether, or thioketo binding sites can
Cyclidenes, and Sepulebrates) wherein all also be included in the
macrocyclic ligand, so Binding Sites are composed of Sulfur and
long as the total number of binding sites is four are contained in
a Combination of 6- to ten. Can include other hydrocarbon/ring
Membered Heterocyclic Rings and Thiol, systems bound to this
macrocyclic ligand, but Thioether, or Thioketo Groups (S--S they do
not coordinate with the stabilized, high Tridentates, S--S
Tetradentates, or S--S valence metal ion. This ligand and/or
attached, Hexadentates) uncoordinating hydrocarbon/rings may or may
not have halogen or polarizing or water- insolubilizing groups
attached. S Valence Stabilizer #18:
RR'--N--C(.dbd.S)--NR''--C(.dbd.S)--NR'''R'''' for Dithiobiurets
(Dithioimidodicarbonic dithiobiurets, and
RR'--N--C(.dbd.S)--NR''--NH-- Diamides), Dithioisobiurets,
Dithiobiureas, C(.dbd.S)--NR'''R'''' for dithiobiureas, where R,
R', Trithiotriurets, Trithiotriureas, R'', R''', and R''''
represent H, NH.sub.2, or any Bis(dithiobiurets),
Bis(dithioisobiurets), organic functional group wherein the number
of Bis(dithiobiureas), Poly(dithiobiurets), carbon atoms ranges
from 0 to 40, optionally Poly(dithioisobiurets), and having halogen
or polarizing or water- Poly(dithiobiureas) (S--S Bidentates, S--S
insolubilizing/solubilizing groups attached. Tridentates, S--S
Tetradentates) Ligand can also contain nonbinding N, O, S, or P
atoms. S Valence Stabilizer #19:
RR'--N--C(.dbd.S)--NR''--C(.dbd.S)--R''' where R, R', R'',
Thioacylthioureas, Thioaroylthioureas, and R''' represent H,
NH.sub.2, or any organic Bis(thioacylthioureas), functional group
wherein the number of carbon Bis(thioaroylthioureas), atoms ranges
from 0 to 40, optionally having Poly(thioacylthioureas), and
halogen or polarizing or water- Poly(thioaroylthioureas) (S--S
Bidentates, insolubilizing/solubilizing groups attached. S--S
Tridentates, S--S Tetradentates) Ligand can also contain nonbinding
N, O, S, or P atoms. S Valence Stabilizer #20:
R--C(.dbd.S)--S--S--C(.dbd.S)--R' where R, and R' Dithioacyl
disulfides, Bis(dithioacyl represent H or any organic functional
group disulfides), and Poly(dithioacyl disulfides) wherein the
number of carbon atoms ranges (S--S Bidentates, S--S Tridentates,
S--S from 0 to 40, optionally having halogen or Tetradentates)
polarizing or water-insolubilizing/solubilizing groups attached.
Ligand can also contain nonbinding N, O, S, or P atoms. S Valence
Stabilizer #21: RR'--N--C(.dbd.S)--S--S--C(.dbd.S)--N--R''R'''
where R, Tetrathioperoxydicarbonic Diamides, R', R'', R'''
represent H or any organic Bis(tetrathioperoxydicarbonic diamides),
functional group wherein the number of carbon and
poly(tetrathioperoxydicarbonic atoms ranges from 0 to 40,
optionally having diamides) (S--S Bidentates, S--S Tridentates,
halogen or polarizing or water- S--S Tetradentates)
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #22:
R--S--C(.dbd.S)--S--S--C(.dbd.S).dbd.S.dbd.R' for Hexathio-,
Pentathio-, and hexathioperoxydicarbonic acids,
R--O--C(.dbd.S)--S-- Tetrathioperoxydicarbonic Acids,
S--C(.dbd.S)--S--R' for pentathioperoxydicarbonic Bis(hexathio-,
pentathio-, and acids, and R--O--C(.dbd.S)--S--S--C(.dbd.S)--O--R'
for tetrathioperoxydicarbonic acids), tetrathioperoxydicarbonic
acids, where R and poly(hexathio-, pentathio-, and R' represent H,
NH.sub.2 or any organic functional tetrathioperoxydicarbonic
acids), and group wherein the number of carbon atoms derivatives
thereof (S--S Bidentates, S--S ranges from 0 to 40, optionally
having halogen Tridentates, S--S Tetradentates) or polarizing or
water- insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #23:
(RR'--N--)(R''R'''--N--)P(.dbd.S)--S--S--P(.dbd.S)(--N--
Dithioperoxydiphosphoramide, R''''R''''')(--N--R''''''R'''''''),
where R, R', R'', R''', Bis(dithioperoxyphosphoramide), and R'''',
R''''', R'''''', and R''''''' represent H, NH.sub.2 or
Poly(dithioperoxydiphosphoramide) (S--S any organic functional
group wherein the Bidentates, S--S Tridentates, S--S number of
carbon atoms ranges from 0 to 40, Tetradentates) optionally having
halogen or polarizing or water-insolubilizing/solubilizing groups
attached. Ligan can also contain nonbinding N, O, S, or P atoms. S
Valence Stabilizer #24:
(R--O--)(R'--O--)P(.dbd.S)--S--S--P(.dbd.S)(--O--R'')(--O--
Dithioperoxydiphosphoric Acids, R''');
(R--O--)(R'--S--)P(.dbd.S)--S--S--P(.dbd.S)(--S--R'')(--
Bis(dithioperoxyphosphoric Acids), O--R'''); or
(R--S--)(R'--S--)P(.dbd.S)--S--S--P(.dbd.S)(--S--
Poly(dithioperoxydiphosphoric Acids), and R')(--S--R'''), where R,
R', R'', R''', R'''', R''''', derivatives thereof (S--S Bidentates,
S--S R'''''', and R''''''' represent H, NH.sub.2 or any
Tridentates, S--S Tetradentates) organic functional group wherein
the number of carbon atoms ranges from 0 to 40, optionally having
halogen or polarizing or water- insolubilizing/solubilizing groups
attached. Ligand can also contain nonbinding N, O, S, or P atoms. S
Valence Stabilizer #25:
(R--O--)(R'--)P(.dbd.S)--NH--P(.dbd.S)(--R'')(--O--R''');
Dithioimidodiphosphonic Acids,
(R--S--)(R'--)P(.dbd.S)--NH--P(.dbd.S)(--R'')(--O--R'''); or
Dithiohydrazidodiphosphonic Acids,
(R--S--)(R'--)P(.dbd.S)--NH--P(.dbd.S)(--R'')(--S--R''') for
Bis(dithioimidodiphosphonic acids), dithioimidodiphosphonic acids,
and NH--NH-- Bis(dithiohydrazidodiphosphonic acids), derivatives
for dithiohydrazidodiphosphonic Poly(dithioimidodiphosphonic
acids), acids, where R, R', R'', and R''' represent H,
Poly(dithiohydrazidodiphosphonic acids), NH.sub.2 or any organic
functional group wherein and derivatives thereof (S--S Bidentates,
S-- the number of carbon atoms ranges from 0 to S Tridentates, and
S--S Tetradentates) 40, optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #26:
(RR'--N--)(R''--)P(.dbd.S)--NH--P(.dbd.S)(--R''')--N--
Dithiolmidodiphosphonamides, R''''R''''') for
dithioimidophosphonamides, and Dithiohydrazidodiphosphonarnides,
(RR'--N--)(R''--)P(.dbd.S)--NH--NH--P(.d- bd.S)(--R''')(--N--
Bis(dithioirnidodiphosphonamides), R''''R''''') for
Bis(dithiohydrazidodiphosphonamides),
dithiohydrazidodiphosphonamides, where R,
Poly(dithioimidodiphosphonamides), and R', R'', R''', R'''', and
R''''' represent H, NH.sub.2 or
Poly(dithiohydrazidodiphosphonamides) any organic functional group
wherein the (S--S Bidentates, S--S Tridentates, S--S number of
carbon atoms ranges from 0 to 40, Tetradentates) optionally having
halogen or polarizing or water-insolubilizing/solubilizing groups
attached. Ligand can also contain nonbinding N, O, S, or P atoms. S
Valence Stabilizer #27:
(RR'--N--)(R''--)P(.dbd.S)-S-P(.dbd.S)(--R''')(--N--
Dithiodiphosphonamides, R''''R'''''), or
(RR'--N--)(R''--)P(.dbd.S)--O--P(.dbd.S)(--
Bis(dithiophosphonarnides), and R''')(N--R''''R'''''), where R, R',
R'', R''', R'''', Poly(dithiodiphosphonamides) (S--S and R'''''
represent H, NH.sub.2 or any organic Bidentates, S--S Tridentates,
S--S functional group wherein the number of carbon Tetradentates)
atoms ranges from 0 to 40, optionally having halogen or polarizing
or water- insolubilizing/solubilizing groups attached. Ligand can
also contain nonbinding N, O, S, or P atoms. S Valence Stabilizer
#28: (R--O--)(R'--)P(.dbd.S)--O--P(.dbd.S)(--R'')(--O--R''');
(R--O--) Dithiodiphosphonic Acids,
(R'--)P(.dbd.S)--S--P(.dbd.S)(--R'')(--O--R'''); (R--S--)(R'--)
Bis(dithioiphosphonic Acids),
P(.dbd.S)--O--P(.dbd.S)(--R'')(--S--R'''); or (R--S--)(R'--)
Poly(dithiodiphosphonic Acids), and
P(.dbd.S)--S--P(.dbd.S)(--R'')(--S--R'''); where R, R', R'',
derivatives thereof (S--S Bidentates, S--S and R''' represent H,
NH.sub.2 or any organic Tridentates, S--S Tetradentates) functional
group wherein the number of carbon atoms ranges from 0 to 40,
optionally having halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #29:
(RR'--N--)(R''--)P(.dbd.S)--S--S--P(.dbd.S)(--R''')(--N--
Dithioperoxydiphosphonamide, R''''R'''''), where R, R', R'', R''',
R'''', and R''''' Bis(dithioperoxyphosphonamide), and represent H,
NH.sub.2 or any organic functional
Poly(dithioperoxydiphosphonamide) (S--S group wherein the number of
carbon atoms
Bidentates, S--S Tridentates, S--S ranges from 0 to 40, optionally
having halogen Tetradentates) or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #30:
(R--O--)(R'--)P(.dbd.S)--S--S--P(.dbd.S)(--R'')(--O--R'''); or
Dithioperoxydiphosphonic Acids,
(R--S--)(R'--)P(.dbd.S)--S--S--P(.dbd.S)(--R'')(--S--R'''),
Bis(dithioperoxyphosphonic Acids), where R, R', R'', and R'''
represent H, NH.sub.2, or Poly(dithioperoxydiphosphonic Acids), and
any organic functional group wherein the derivatives thereof (S--S
Bidentates, S--S number of carbon atoms ranges from 0 to 40,
Tridentates, S--S Tetradentates) optionally having halogen or
polarizing or water-insolubilizing/solubilizing groups attached.
Ligand can also contain nonbinding N, O, S, or P atoms. S Valence
Stabilizer #31: (O.dbd.)PR(--S--R')(--S--R'') or
(S.dbd.)PR(--S--R')(--O-- Dithiophosphonic Acids R''), where R, R',
and R'' represent H, NH.sub.2 or (Phosphonodithioic Acids), any
organic functional group wherein the Bis(dithiophosphonic Acids),
number of carbon atoms ranges from 0 to 40, Poly(dithiophosphonic
Acids), and optionally having halogen or polarizing or derivatives
thereof (S--S Bidentates, S--S water-insolubilizing/solubilizing
groups Tridentates, S--S Tetradentates) attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #32:
(S.dbd.)PR(--S--R')(--S--R''), where R, R', and R''
Trithiophosphonic Acids represent H, NH.sub.2 or any organic
functional (Phosphonotrithioic Acids), group wherein the number of
carbon atoms Bis(trithiophosphonic Acids), ranges from 0 to 40,
optionally having halogen Poly(trithiophosphonic Acids), and or
polarizing or water- derivatives thereof (S--S Bidentates, S--S
insolubilizing/solubilizing groups attached. Tridentates, S--S
Tetradentates) Ligand can also contain nonbinding N, O, S, or P
atoms. S Valence Stabilizer #33: (O.dbd.)PR(--S--S--R')(--S--R'')
or (S.dbd.)PR(--S--S--R') Phosphono(dithioperoxo)thioic Acids),
(--O--R''), where R, R', and R'' represent H, NH.sub.2
Bis[phosphono(dithioperoxo)thioic Acids], or any organic functional
group wherein the Poly[phosphono(dithioperoxo)thioic number of
carbon atoms ranges from 0 to 40, Acids], and derivatives thereof
(S--S optionally having halogen or polarizing or Bidentates, S--S
Tridentates, S--S water-insolubilizing/solubilizing groups
Tetradentates) attached. Ligand can also contain nonbinding N, O,
S, or P atoms. S Valence Stabilizer #34:
(S.dbd.)PR(--S--S--R')(--S--R''), where R, R', and R''
Phosphono(dithioperoxo)dithioic Acids), represent H, NH.sub.2 or
any organic functional Bis[phosphono(dithioperoxo)dithioic group
wherein the number of carbon atoms Acids], ranges from 0 to 40,
optionally having halogen Polyl[phosphono(dithioperoxo)dithioic or
polarizing or water- Acids], and derivatives thereof (S--S
insolubilizing/solubilizing groups attached. Bidentates, S--S
Tridentates, S--S Ligand can also contain nonbinding N, O, S, or
Tetradentates) P atoms. S Valence Stabilizer #35: R--S--R'CSOH or
R--S--R'CSSH for S- S-(Alkylthio)thiocarboxylic Acids, S-
(alkylthio)thiocarboxylic and S- (Arylthio)thiocarboxylic Acids,
and S,S- (arylthio)thiocarboxylic acids, and HSOCR--S--
thiobisthiocarboxylic Acids (S--S Bidentates R'COSH or
HSSCR--S--R'CSSH for S,S- and S--S Tridentates)
thiobisthiocarboxylic acids, where R and R' represent H or any
organic functional group wherein the number of carbon atoms ranges
from 0 to 40, optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #36:
R--S--S--R'CSOH or R--S--S--R'CSSH for S--
S-(Alkyldisulfido)thiocarboxylic Acids, S- (alkyldi
sulfido)thiocarboxylic and S-- (Aryldisulfido)thiocarboxylic Acids,
and (aryldisulfido)thiocarboxylic acids, and
S,S'--Disulfidobisthiocarboxylic Acids (S--S HSOCR--S--S--R'COSH or
HSSCR--S--S--R'CSSH Bidentates and S--S Tridentates) for
S,S'--disulfidobisthiocarboxylic acids, where R and R' represent H
or any organic functional group wherein the number of carbon atoms
ranges from 0 to 40, optionally having halogen or polarizing or
water- insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #37:
R--CH(--SR'')--CH(--SR''')--R', and R--C(-- 1,2-Dithiolates,
Bis(1,2-dithiolates), and SR'').dbd.C(--SR''')--R', where R, R',
R'', and R''' Poly(1,2-dithiolates) (S--S Bidentates, S--S
represent H, NH.sub.2 or any organic functional Tridentates, S--S
Tetradentates) group wherein the number of carbon atoms ranges from
0 to 40, optionally having halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #38:
RN--C(.dbd.O)--CHR'--S--C(.dbd.S) for rhodanines, and Rhodanines
and Bis(rhodanines) (S--S
R--[N--C(.dbd.O)--CHR'--S--C(.dbd.S)].sub.2 for Bidentates and S--S
Tetradentates) bis(rhodanines), where R and R' represent H,
NH.sub.2 or any organic functional group wherein the number of
carbon atoms ranges from 0 to 40, optionally having halogen or
polarizing or water-insolubilizing/solubilizing groups attached.
Ligand can also contain nonbinding N, O, S, or P atoms. S Valence
Stabilizer #39: RN--C(SH)(SH), where R represents H, NH.sub.2 or
Dithiocarbimates, Bis(dithiocarbimates), any organic functional
group wherein the and Poly(dithiocarbimates) (S--S Bidentates,
number of carbon atoms ranges from 0 to 40, S--S Tridentates, and
S--S Tetradentates) optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups N, O, S, or P atoms. S
Valence Stabilizer #40: RS.sup.+.dbd.C(SH)(SH) or
RS--C(.dbd.S)(SH), where R Thioxanthates, Bis(thioxanthates), and
represents H, NH.sub.2 or any organic functional
Poly(thioxanthates) (S--S Bidentates and S-- group wherein the
number of carbon atoms S Tetradentates) ranges from 0 to 40,
optionally having halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #41:
RO.sup.+.dbd.C(SH)(SH) or RO--C(.dbd.S)(SH), where R Xanthates,
Bis(xanthates), and represents H, NH.sub.2 or any organic
functional Poly(xanthates) (S--S Bidentates and S--S group wherein
the number of carbon atoms Tetradentates) ranges from 0 to 40,
optionally having halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #42:
Typically RR'R''P.dbd.C(SH)(SH) [pentavalent P],
Phosphinodithioformates (S--S Bidentates) although
RR'P--C(.dbd.S)(SH) [trivalent P] may be acceptable in some
situations, where R, R', and R'' represent H, NH.sub.2 or any
organic functional group wherein the number of carbon atoms ranges
from 0 to 40, optionally having halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #43:
R--S--C(--S--R'')--O--R' for dithioborates, R--S--C Alkyl- and
Aryl- Dithioborates, (--S--R'')--S--R' for trithioborates, and
R--S--S--C(S-- Trithioborates, Perthioborates, R'')--S--R' for
perthioborates, where R, R', and Bis(dithioborates),
Bis(trithioborates), and R'' represent H, NH.sub.2 or any organic
functional Bis(perthioborates) (S--S Bidentates and group wherein
the number of carbon atoms S--S Tetradentates) ranges from 0 to 40,
optionally having halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #44:
R--C(--S--R'')--S--R', where R, R', and R'' Alkyl- and Aryl-
Dithioboronates, and represent H, NH.sub.2 or any organic
functional Bis(dithioboronates) (S--S Bidentates and group wherein
the number of carbon atoms S--S Tetradentates) ranges from 0 to 40,
optionally having halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #45:
(O.dbd.)As(--S--R)(--S--R')(--S--R'') or (S.dbd.)As(--S--R)
Trithioarsonic Acids (Arsonotrithioic (--S--R')(--O--R'') for
trithioarsonic acid; (O.dbd.)As Acids), Dithioarsonic Acids
(--O--R)(--S--R')(--S--R'') or (S.dbd.)As(--S--R)(--O--R')
(Arsonodithioic Acids), Tetrathioarsonic (--O--R'') for
dithioarsonic acid, or (S.dbd.)As(--S--R) Acids (Arsonotetrathioic
Acids), and (--S--R')(--S--R'') for tetrathioarsonic acid, where
derivatives thereof (S--S Bidentates, S--S R, R', and R'' represent
H, NH.sub.2 or any organic Tridentates, S--S Tetradentates)
functional group wherein the number of carbon atoms ranges from 0
to 40, optionally having halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #46:
(O.dbd.)Sb(--S--R)(--S--R')(--S--R'') or (S.dbd.)Sb(--S--R)
Trithioantimonic Acids (Stibonotrithioic (--S--R')(--O--R'') for
trithioantimonic acid; Acids), Dithioantimonic Acids
(O.dbd.)Sb(--O--R)(--S--R')(--S--R'') or (S.dbd.)Sb(--S--R)
(Stibonodithioic Acids), (--O--R')(--O--R'') for dithioantimonic
acid, or Tetrathioantimonic Acids
(S.dbd.)Sb(--S--R)(--S--R')(--S--R'') for (Stibonotetrathioic
Acids), and derivatives tetrathioantimonic acid, where R, R', and
R'' thereof (S--S Bidentates, S--S Tridentates, represent H,
NH.sub.2 or any organic functional S--S Tetradentates) group
wherein the number of carbon atoms ranges from 0 to 40, optionally
having halogen or polarizing or water- insolubilizing/solubilizing
groups attached. Ligand can also contain nonbinding N, O, S, or P
atoms. S Valence Stabilizer #47: RR'R''P.dbd.S for phosphine
P-sulfides, and Phosphine P-sulfides and Amino-
(RR'N)(R''R'''N)(R''''R'''''N)P.dbd.S for amino- substituted
Phosphine sulfides (S substituted phosphine sulfides, where R, R',
R'', Monodentates) R''', R'''', and R''''' represent H, Cl, Br,
NH.sub.2 or any organic functional group wherein the number of
carbon atoms ranges from 0 to 40, optionally having halogen or
polarizing or water-insolubilizing/solubilizing groups attached.
(Rs are typically aromatic or heterocyclic for phosphine
P-sulfides.) Ligand can also contain nonbinding N, O, S, or P
atoms. S Valence Stabilizer #48: RR'R''As.dbd.S for arsine
As-sulfides, and Arsine As-sulfides and Amino-substituted
(RR'N)(R''R'''N)(R''''R'''''N)As.dbd.S for amino- Arsine sulfides
(S Monodentates) substituted arsine sulfides, where R, R', R'',
R''', R'''', and R''''' represent H, Cl, Br, NH.sub.2 or
any organic functional group wherein the number of carbon atoms
ranges from 0 to 40, optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. (Rs are
typically aromatic or heterocyclic for arsine As-sulfides.) Ligand
can also contain nonbinding N, O, S, or P atoms. S Valence
Stabilizer #49: Thiocyanates bound directly to the high valence
Thiocyanate ligands (S Monodentates) metal ion. S Valence
Stabilizer #50: Thiols (HS--R, HS--R--SH, etc.), where R and R'
Thiolates (S Monodentates) represent H or any organic functional
group wherein the number of carbon atoms ranges from 0 to 35,
optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. S Valence
Stabilizer #51: Sulfide (--S.sup.2-) ligands bound directly to the
high Sulfide ligands (S Monodentates) valence metal ion. P Valence
Stabilizer #1: PH.sub.3, PH.sub.2R, PHR.sub.2, and PR.sub.3 where R
represents Monophosphines (P Monodentates) H or any organic
functional group wherein the wherein at least one Phosphorus Atom
is a number of carbon atoms ranges from 0 to 35, Binding Site
optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, P, As, O, S, or Se atoms. P Valence
Stabilizer #2: R'--P--R--P--R'', where R, R', and R'' represent H
Diphosphines (a P--P Bidentate) wherein at or any organic
functional group wherein the least one Phosphorus Atom is a Binding
number of carbon atoms ranges from 0 to 35, Site optionally having
halogen or polarizing or water-insolubilizing/solubilizing groups
N, P, As, O, S, or Se atoms. P Valence Stabilizer #3:
R--P--R'--P--R''--P--R''', where R, R', R'', and R''' Triphosphines
(either P--P Bidentates or represent H or any organic functional
group P--P--P Tridentates) wherein at least one wherein the number
of carbon atoms ranges Phosphorus Atom is a Binding Site from 0 to
35, optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, P, As, O, S, or Se atoms. P Valence
Stabilizer #4: R--P--R'--P--R''--P--R'''--P--R'''', where R, R',
R'', Tetraphosphines (P--P Bidentates, P--P R''', and R''''
represent H or any organic Tridentates, or P--P Tetradentates)
wherein functional group wherein the number of carbon at least one
Phosphorus Atom is a Binding atoms ranges from 0 to 35, optionally
having Site halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, P, As, O, S, or Se atoms. P Valence
Stabilizer #5: R--P--R'--P--R''--P--R'''--P--R''''--P--R''''',
where R, Pentaphosphines (P--P Bidentates, P--P R', R'', R''',
R'''', and R''''' represent H or any Tridentates, or P--P
Tetradentates) wherein organic functional group wherein the number
of at least one Phosphorus Atom is a Binding carbon atoms ranges
from 0 to 35, optionally Site having halogen or polarizing or
water- insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, P, As, O, S, or Se atoms. P Valence
Stabilizer #6: Hexaphosphines (P--P Bidentates, P--P where R, R',
R'', R''', R'''', R''''', and R'''''' Tridentates, P--P
Tetradentates, or P--P represent H or any organic functional group
Hexadentates) wherein at least one wherein the number of carbon
atoms ranges Phosphorus Atom is a Binding Site from 0 to 35,
optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, P, As, O, S, or Se atoms. P Valence
Stabilizer #7: Five membered heterocyclic ring containing
Five-Membered Heterocyclic Rings one, two, or three phosphorus
atoms, all of containing One, Two, or Three Phosphorus which may or
may not function as binding sites. Atoms wherein at least one
Phosphorus Can include other ring systems bound to this Atom is a
Binding Site (P Monodentates or heterocyclic ring, but they do not
coordinate P--P Bidentates) with the stabilized, high valence metal
ion. Ring can also contain O, S, N, As, or Se atoms. This
5-membered ring and/or attached, uncoordinating rings may or may
not have halogen or polarizing or water-
insolubilizing/solubilizing groups attached. P Valence Stabilizer
#8: Six membered heterocyclic ring containing one, Six-Membered
Heterocyclic Rings two, or three phosphorus atoms, all of which
containing One, Two, or Three Phosphorus may or may not function as
binding sites. Can Atoms wherein at least one Phosphorus include
other ring systems bound to this Atom is a Binding Site (P
Monodentates or heterocyclic ring, but they do not coordinate P--P
Bidentates) with the stabilized, high valence metal ion. Ring can
also contain O, S, N, As, or Se atoms. This 6-membered ring and/or
attached, uncoordinating rings may or may not have halogen or
polarizing or water- insolubilizing/solubilizing groups attached. P
Valence Stabilizer #9: Five membered heterocyclic ring(s)
containing Five-Membered Heterocyclic Rings one, two, or three
phosphorus atoms. In containing One, Two, or Three Phosphorus
addition, ligand contains additional Atoms at least one additional
Phosphorus phosphorus-containing substituents (usually Atom Binding
Site not in a Ring (P phosphines) that constitute P binding sites.
Can Monodentates, P--P Bidentates, P--P include other ring systems
bound to the Tridentates, P--P Tetradentates, or P--P heterocyclic
ring or to the P-containing Hexadentates) substituent, but they do
not coordinate with the stabilized, high valence metal ion. Ring(s)
can also contain O, N, S, As or Se atoms. This 5- membered ring(s)
and/or attached, uncoordinating rings and/or P-containing
substituent(s) may or may not have halogen or polarizing or
water-insolubilizing/solubilizing groups attached. P Valence
Stabilizer #10: Six membered heterocyclic ring(s) containing
Six-Membered Heterocyclic Rings one, two, or three phosphorus
atoms. In containing One, Two, or Three Phosphorus addition, ligand
contains additional Atoms at least one additional Phosphorus
phosphorus-containing substituents (usually Atom Binding Site not
in a Ring (P phosphines) that constitute P binding sites. Can
Monodentates, P--P Bidentates, P--P include other ring systems
bound to the Tridentates, P--P Tetradentates, or P--P heterocyclic
ring or to the P-containing Hexadentates) substituent, but they do
not coordinate with the stabilized, high valence metal ion. Ring(s)
can also contain O, N, S, As or Se atoms. This 6- membered ring(s)
and/or attached, uncoordinating rings and/or P-containing
substituent(s) may or may not have halogen or polarizing or
water-insolubilizing/solubilizing groups attached. P Valence
Stabilizer #11: Five membered heterocyclic ring(s) containing
Five-Membered Heterocyclic Rings one, two, or three phosphorus
atoms. In containing One, Two, or Three Phosphorus addition, ligand
contains additional Atoms at least one additional Phosphorus
phosphorus-containing rings that constitute P Atom Binding Site in
a separate Ring (P binding sites. Can include other ring systems
Monodentates, P--P Bidentates, P--P bound to the P-containing
heterocyclic rings, Tridentates, P--P Tetradentates, or P--P but
they do not coordinate with the stabilized, Hexadentates) high
valence metal ion. Ring(s) can also contain O, N, S, As, or Se
atoms. This 5- membered ring(s) and/or additional P- containing
ring(s) and/or attached, uncoordinating rings may or may not have
halogen or polarizing or water- insolubilizing/solubilizing groups
attached. P Valence Stabilizer #12: Six membered heterocyclic
ring(s) containing Six-Membered Heterocyclic Rings one, two, or
three phosphorus atoms. In containing One, Two, or Three Phosphorus
addition, ligand contains additional Atoms at least one additional
Phosphorus phosphorus-containing rings that constitute P Atom
Binding Site in a separate Ring (P binding sites. Can include other
ring systems Monodentates, P--P Bidentates, P--P bound to the
P-containing heterocyclic rings, Tridentates, P--P Tetradentates,
or P--P but they do not coordinate with the stabilized,
Hexadentates) high valence metal ion. Ring(s) can also contain O,
N, S, As, or Se atoms. This 6- membered ring(s) and/or additional
P- containing ring(s) and/or attached, uncoordinating rings may or
may not have halogen or polarizing or water-
insolubilizing/solubilizing groups attached. P Valence Stabilizer
#13: Macrocyclic ligands containing two, three, four, Two-, Three-,
Four-, Five-, Six-, and Eight- five, six, or eight phosphorus
binding sites to Membered Macrocyclics, Macrobicyclics, valence
stabilize the central metal ion. Can and Macropolycyclics
(including include other hydrocarbon or ring systems Catapinands,
Cryptands, Cyclidenes, and bound to this macrocyclic ligand, but
they do Sepulchrates) wherein all Binding Sites are not coordinate
with the stabilized, high valence composed of Phosphorus and are
not metal ion. This ligand and/or attached, contained in Component
Heterocyclic uncoordinating hydrocarbons/rings may or may Rings
(P--P Bidentates, P--P Tridentates, P--P not have halogen or
polarizing or water- Tetradentates, and P--P Hexadentates)
insolubilizing/solubilizing groups attached. P Valence Stabilizer
#14: Macrocyclic ligands containing a total of four, Four-, Six-,
or Eight-Membered six, or eight five-membered heterocyclic rings
Macrocyclics, Macrobicyclics, and containing phosphorus binding
sites. Can Macropolycyclics (including Catapinands, include other
hydrocarbon/ring systems bound Cryptands, Cyclidenes, and
Sepulchrates) to this macrocyclic ligand, but they do not wherein
all Binding Sites are composed of coordinate with the stabilized,
high valence Phosphorus and are contained in metal ion. This ligand
and/or attached, Component 5-Membered Heterocyclic uncoordinating
hydrocarbon/rings may or may Rings (P--P Tridentates, P--P
Tetradentates, not have halogen or polarizing or water- or P--P
Hexadentates) insolubilizing groups attached. P Valence Stabilizer
#15: Macrocyclic ligands containing at least one 5- Four-, Six-, or
Eight-Membered membered heterocyclic ring. These Macrocyclics,
Macrobicyclics, and heterocyclic rings provide phosphorus binding
Macropolycyclics (including Catapinands, sites to valence stabilize
the central metal ion. Cryptands, Cyclidenes, and Sepulchrates)
Other phosphine binding sites can also be wherein all Binding Sites
are composed of included in the macrocyclic ligand, so long as
Phosphorus and are contained in a the total number of binding sites
is four, six, or Combination of 5-Membered Heterocyclic eight. Can
include other hydrocarbon/ring Rings and Phosphine Groups (P--P
systems bound to this macrocyclic ligand, but Tridentates, P--P
Tetradentates, or P--P they do not coordinate with the stabilized,
high Hexadentates) valence metal ion. This ligand and/or attached,
uncoordinating hydrocarbon/rings may or may not have halogen or
polarizing or water- insolubilizing groups attached. P Valence
Stabilizer #16: Macrocyclic ligands containing a total of four,
Four-, Six-, or Eight-Membered six, or eight six-membered
heterocyclic rings Macrocyclics, Macrobicyclics, and containing
phosphorus binding sites. Can Macropolycyclics (including
Catapinands, include other hydrocarbon/ring systems bound
Cryptands, Cyclidenes, and Sepulchrates) to this macrocyclic
ligand, but they do not wherein all Binding Sites are composed of
coordinate with the stabilized, high valence Phosphorus and are
contained in metal ion. This ligand and/or attached, Component
6-Membered Heterocyclic uncoordinating hydrocarbon/rings may or may
Rings (P--P Tridentates, P--P Tetradentates, not have halogen or
polarizing or water- or P--P Hexadentates) insolubilizing groups
attached. P Valence Stabilizer #17: Macrocyclic ligands containing
at least one 6- Four-, Six-, or Eight-Membered membered
heterocyclic ring. These Macrocyclics, Macrobicyclics, and
heterocyclic rings provide phosphorus binding Macropolycyclics
(including Catapinands, sites to valence stabilize the central
metal ion. Cryptands, Cyclidenes, and Sepulchrates) Other phosphine
binding sites can also be wherein all Binding Sites are composed of
included in the macrocyclic ligand, so long as Phosphorus and are
contained in a the total number of binding sites is four, six, or
Combination of 6-Membered Heterocyclic eight. Can include other
hydrocarbon/ring Rings and Phosphine Groups (P--P systems bound to
this macrocyclic ligand, but Tridentates, P--P Tetradentates, or
P--P they do not coordinate with the stabilized, high Hexadentates)
valence metal ion. This ligand and/or attached, uncoordinating
hydrocarbon/rings may or may not have halogen or polarizing or
water- insolubilizing groups attached. O Valence Stabilizer #1:
RR'--N--C(.dbd.O)--NR''--C(.dbd.O)--NR'''R'''' for Biurets
(Imidodicarbonic Diamides), biurets, and
RR'--N--C(O)--NR''--NH--C(O)-- Isobiurets, Biureas, Triurets,
Triureas, NR'''R'''' for biureas, where R, R', R'', R''', and
Bis(biurets), Bis(isobiurets), Bis(biureas), R'''' represent H,
NH.sub.2 or any organic functional Poly(biurets), Poly(isobiurets),
and group wherein the number of carbon atoms Poly(biureas) (O--O
Bidentates, O--O ranges from 0 to 40, optionally having halogen
Tridentates, O--O Tetradentates) or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. O Valence Stabilizer #2:
RR'--N--C(.dbd.O)--NR''--C(.dbd.O)--R''' where R, R', Acylureas,
Aroylureas, Bis(acylureas), R'', and R''' represent H, NH.sub.2 or
any organic Bis(aroylureas), Poly(acylureas), and functional group
wherein the number of carbon Poly(aroylureas) (O--O Bidentates,
O--O atoms ranges from 0 to 40, optionally having Tridentates, O--O
Tetradentates) halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. O Valence Stabilizer #3:
RC(.dbd.O)--NR'--C(O)--R'' for imidodialdehydes, Imidodialdehydes,
Hydrazidodialdehydes and RC(.dbd.O)--NR'--NH--C(.dbd.0)--R'' for
(Acyl hydrazides), Bis(imidodialdehydes), hydrazidodialdehydes
(acyl hydrazides), where Bis(hydrazidodialdehydes), R, R', and R''
represent H, NH.sub.2, or any organic Poly(imidodialdehydes), and
functional group wherein the number of carbon
Poly(hydrazidodialdehydes) (O--O atoms ranges from 0 to 40,
optionally having Bidentates, O--O Tridentates, O--O halogen or
polarizing or water- Tetradentates) insolubilizing/solubilizing
groups attached. Ligand can also contain nonbinding N, O, S, or P
atoms. O Valence Stabilizer #4: R--O--C(.dbd.O)--NR'--C(O)--O--R''
for Imidodicarbonic acids, imidodicarbonic acids, and
R--O--C(.dbd.O)--NR'-- Hydrazidodicarbonic acids,
NH--C(.dbd.O)--O--R'' for hydrazidodicarbonic acids,
Bis(imidodicarbonic acids), where R, R', and R'' represent H,
NH.sub.2, or any Bis(hydrazidodicarbonic acids), organic functional
group wherein the number of Poly(imidodicarbonic acids), carbon
atoms ranges from 0 to 40, optionally Poly(hydrazidodicarbonic
acids) and having halogen or polarizing or water- derivatives
thereof (O--O Bidentates, O--O insolubilizing/solubilizing groups
attached. Tridentates, O--O Tetradentates) Ligand can also contain
nonbinding N, O, S, or P atoms. O Valence Stabilizer #5:
RR'--N--S(.dbd.O)(.dbd.O)--NR''--S(.dbd.O)(.dbd.O)--NR'''R''''
Imidodisulfamic Acid, Irnidodisulfuric for imidodisulfamic acid,
and R--O--S(.dbd.O)(.dbd.O)-- Acid, Bis(Imidodisulfamic Acid),
NR'--S(.dbd.O)(.dbd.O)--OR'' for imidosulfuric acid,
Bis(Imidodisulfuric Acid), where R, R', and R'' represent H,
NH.sub.2, or any Poly(Imidodisulfamic Acid), and organic functional
group wherein the number of Poly(Imidodisulfuric Acid) and
derivatives carbon atoms ranges from 0 to 40, optionally thereof
(O--O Bidentates, O--O Tridentates, having halogen or polarizing or
water- O--O Tetradentates) insolubilizing/solubilizing groups
attached. Ligand can also contain nonbinding N, O, S, or P atoms. O
Valence Stabilizer #6: R--C(.dbd.O)--CR'R''--C(.dbd.O)--R''' where
R, R', R'', 1,3-Diketones (Beta-Diketonates), 1,3,5- and R'''
represent H, NH.sub.2, or any organic Triketones,
Bis(1,3-Diketones), and functional group wherein the number of
carbon Poly(1,3-Diketones), all with a Molecular atoms ranges from
0 to 40, optionally having Weight Greater than 125 (O--O
Bidentates, halogen or polarizing or water- O--O Tridentates, O--O
Tetradentates) insolubilizing/solubilizing groups attached. Ligand
can also contain nonbinding N, O, S, or P atoms. If these ligands
exhibit a molecular weight less than or equal to 125, the
solubility of the resultant Co.sup.+3-diketonate complex will be
too high. O Valence Stabilizer #7: R--C(.dbd.O)--C(.dbd.O)--R'
where R and R' represent 1,2-Diketones (Alpha-Diketonates), 1,2,3-
H, NH.sub.2, or any organic functional group Triketones,
Tropolonates, ortho-Quinones, wherein the number of carbon atoms
ranges Bis(1,2-Diketones), and Poly(1,2- from 0 to 40, optionally
having halogen or Diketones), all with a Molecular Weight
polarizing or water-insolubilizing/solubilizing Greater than 100
(O--O Bidentates, O--O groups attached. Ligand can also contain
Tridentates, O--O Tetradentates) nonbinding N, O, S, or P atoms. If
these ligands exhibit a molecular weight less than or equal to 100,
the solubility of the resultant Co.sup.+3-diketonate complex will
be too high. O Valence Stabilizer #8:
RR'--N--C(.dbd.O)--CR''R'''--C(.dbd.O)--N--R''''R''''' Malonamides
(Malonodiamides), where R, R', R'', R''', R'''', and R'''''
represent Bis(malonamides), and Polymalonamides H, NH.sub.2, or any
organic functional group (O--O Bidentates, O--O Tridentates, O--O
wherein the number of carbon atoms ranges Tetradentates) from 0 to
40, optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. O Valence Stabilizer #9:
RR'--N--C(.dbd.O)--CR''R'''--C(.dbd.O)--R'''' where R,
2-Acylacetamides, Bis(2-acylacetamides), R', R'', R''', and R''''
represent H, NH.sub.2, or any and Poly(2-acylacetamides) (O--O
organic functional group wherein the number of Bidentates, O--O
Tridentates, O--O carbon atoms ranges from 0 to 40, optionally
Tetradentates) having halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. O Valence Stabilizer #10:
RR'--N--C(.dbd.O)--S--C(.dbd.O)--N--R''R''' where R, R',
Monothiodicarbonic Diamides, R'', and R''' represent H, NH.sub.2 or
any organic Bis(monothiodicarbonic diamides), and functional group
wherein the number of carbon Poly(monothiodicarbonic diamides)
(O--O atoms ranges from 0 to 40, optionally having Bidentates, O--O
Tridentates, O--O halogen or polarizing or water- Tetradentates)
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. O Valence Stabilizer #11:
R--O--C(.dbd.O)--S--C(.dbd.O)--O--R', where R and R'
Monothiodicarbonic Acids, represent H, NH.sub.2 or any organic
functional Bis(monothiodicarbonic acids), group wherein the number
of carbon atoms Poly(monothiodicarbonic acids), and ranges from 0
to 40, optionally having halogen derivatives thereof (O--O
Bidentates, O--O or polarizing or water- Tridentates, O--O
Tetradentates) insolubilizing/solubilizing groups attached. Ligand
can also contain nonbinding N, O, S, or P atoms. O Valence
Stabilizer #12: R--O--C(.dbd.O)--S--S--C(.dbd.O)--O--R', where R
and R' Dithioperoxydicarbonic Acids, represent H, NH.sub.2 or any
organic functional Bis(dithioperoxydicarbonic acids), group wherein
the number of carbon atoms poly(dithioperoxydicarbonic acids), and
ranges from 0 to 40, optionally having halogen derivatives thereof
(O--O Bidentates, O--O or polarizing or water- Tridentates, O--O
Tetradentates) insolubilizing/solubilizing groups attached. Ligand
can also contain nonbinding N, O, S, or P atoms. O Valence
Stabilizer #13:
R--O--S(.dbd.O)(.dbd.O)--S--S(.dbd.O)(.dbd.O)--O--R', where R
Trithionic acid, Bis(trithionic acid), and R' represent H, NH.sub.2
or any organic Poly(trithionic acid), and derivatives functional
group wherein the number of carbon thereof (O--O Bidentates, O--O
Tridentates, atoms ranges from 0 to 40, optionally having O--O
Tetradentates) halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. O Valence Stabilizer #14:
(R--O--)(R'--O--)P(.dbd.O)--P(.dbd.O)(--O--R'')(--O--R'''),
Hypophosphoric Acids, where R, R', R'', and R''' represent H,
NH.sub.2 or Bis(hypophosphoric acids), and any organic functional
group wherein the Poly(hypophosphoric acids), and number of carbon
atoms ranges from 0 to 40, derivatives thereof (O--O Bidentates,
O--O optionally having halogen or polarizing or Tridentates, O--O
Tetradentates) water-insolubilizing/solubilizing groups attached.
Ligand can also contain nonbinding N, O, S, or P atoms. Note: these
ligands are not to be confused with hypophosphorous acid
derivatives (hypophosphites) (R--O--) R''R'''P(.dbd.O) which are
very reducing and therefore unacceptable for stabilization of high
valence states in metal ions. O Valence Stabilizer #15:
(RR'--N--)(R''R'''--N--)P(.dbd.O)--P(.dbd.O)(--N--
Hypophosphoramides, R''''R''''')(--N--R''''''R'''''''), where R,
R', R'', R''', Bis(hypophosphoramides), and R'''', R''''', R'''''',
and R''''''' represent H, NH.sub.2 or Poly(hypophosphoramides)
(O--O any organic functional group wherein the Bidentates, O--O
Tridentates, O--O number of carbon atoms ranges from 0 to 40,
Tetradentates) optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. Note: these ligands are not
to be confused with hypophosphorous acid derivatives
(hypophosphites) (R--O--) R''R'''P(.dbd.O) which are very reducing
and therefore unacceptable for stabilization of high valence states
in metal ions.
O Valence Stabilizer #16:
(R--O--)(R'--O--)P(.dbd.O)--NH--P(.dbd.O)(--O--R'')(--O--
Imidodiphosphoric Acids, R''') for imidodiphosphoric acids, and
(R--O--) Hydrazidodiphosphoric Acids,
(R'--O--)P(.dbd.O)--NH--NH--P(.dbd.O)(--O--R'')(--O--R''')
Bis(imidodiphosphoric Acids), for hydrazidodiphosphoric acids;
where R, R', Bis(hydrazidodiphosphoric Acids), R'', and R'''
represent H, NH.sub.2 or any organic Poly(imidodiphosphoric Acids),
functional group wherein the number of carbon
Poly(hydrazidodiphosphoric Acids), and atoms ranges from 0 to 40,
optionally having derivatives thereof (O--O Bidentates, O--O
halogen or polarizing or water- Tridentates, O--O Tetradentates)
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. O Valence Stabilizer #17:
(RR'--N--)(R''R'''--N--)P(.dbd.O)--NH--P(.dbd.O)(--N--
Imidodiphosphoramides, R''''R''''')(--N--R''''''R''''''') for
Hydrazidodiphosphoramides, imidodiphosphoramides, and --NH--NH--
Bis(imidodiphosphoramides), derivatives for
hydrazidodiphosphoramides, Bis(hydrazidodiphosphoramides), where R,
R', R'', R''', R'''', R''''', R'''''', and
Poly(imidodiphosphoramides), and R''''''' represent H, NH.sub.2 or
any organic Poly(hydrazidodiphosphoramides) (O--O functional group
wherein the number of carbon Bidentates, O--O Tridentates, O--O
atoms ranges from 0 to 40, optionally having Tetradentates) halogen
or polarizing or water- insolubilizing/solubilizing groups
attached. Ligand can also contain nonbinding N, O, S, or P atoms. O
Valence Stabilizer #18:
(RR'--N--)(R''R'''--N--)P(.dbd.O)--O--P(.dbd.O)(--N--
Diphosphoramides, R''''R''''')(--N--R''''''R'''''''), where R, R',
R'', R''', Bis(diphosphoramides), and R'''', R''''', R'''''', and
R''''''' represent H, NH.sub.2 or Poly(diphosphoramides) (O--O
Bidentates, any organic functional group wherein the O--O
Tridentates, O--O Tetradentates) number of carbon atoms ranges from
0 to 40, optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. O Valence Stabilizer #19:
(R--O--)(R'--)P(.dbd.O)--NH--P(.dbd.O)(--R'')(--O--R''') for
Imidodiphosphonic Acids, imidodiphosphonic acids, and
(R--O--)(R'--) Hydrazidodiphosphonic Acids,
P(.dbd.O)--NH--NH--P(.dbd.O)(--R'')(--O--R''') for
Bis(imidodiphosphonic Acids), hydrazidodiphosphonic acids; where R,
R', R'', Bis(hydrazidodiphosphonic Acids), and R''' represent H,
NH.sub.2 or any organic Poly(imidodiphosphonic Acids), functional
group wherein the number of carbon Poly(hydrazidodiphosphonic
Acids), and atoms ranges from 0 to 40, optionally having
derivatives thereof (O--O Bidentates, O--O halogen or polarizing or
water- Tridentates, O--O Tetradentates) insolubilizing/solubilizing
groups attached. Ligand can also contain nonbinding N, O, S, or P
atoms. O Valence Stabilizer #20:
(RR'--N--)(R''--)P(.dbd.O)--NH--P(.dbd.O)(--R''')(--N--
Imidodiphosphonamides, R''''R''''') for imidodiphosphonamides, and
Hydrazidodiphosphonamides, --NH--NH-- derivatives for
Bis(imidodiphosphonamides), hydrazidodiphosphonamides, where R, R',
R'', Bis(hydrazidodiphosphonamides), R''', R'''', and R'''''
represent H, NH.sub.2 or any Poly(imidodiphosphonamides), and
organic functional group wherein the number of
Poly(hydrazidodiphosphonamides) (O--O carbon atoms ranges from 0 to
40, optionally Bidentates, O--O Tridentates, O--O having halogen or
polarizing or water- Tetradentates) insolubilizing/solubilizing
groups attached. Ligand can also contain nonbinding N, O, S, or P
atoms. O Valence Stabilizer #21:
(RR'--N--)(R''--)P(.dbd.O)--O--P(.dbd.O)(--R''')(--N--
Diphosphonamides, R''''R'''''), where R, R', R'', R''', R'''', and
R''''' Bis(diphosphonamides), and represent H, NH.sub.2 or any
organic functional Poly(diphosphonamides) (O--O Bidentates, group
wherein the number of carbon atoms O--O Tridentates, O--O
Tetradentates) ranges from 0 to 40, optionally having halogen or
polarizing or water- insolubilizing/solubilizing groups attached.
Ligand can also contain nonbinding N, O, S, or P atoms. O Valence
Stabilizer #22: R--CR'(--OH)--CH.sub.2--C(.dbd.O)--R'', where R,
R', and Beta-Hydroxyketones, Beta- R'' represent H, NH--, or any
organic functional Hydroxyaldehydes, Bis(beta- group wherein the
number of carbon atoms hydroxyketones), Bis(beta- ranges from 0 to
40, optionally having halogen hydroxyaldehydes), Poly(beta- or
polarizing or water- hydroxyketones), and Poly(beta-
insolubilizing/solubilizing groups attached. hydroxyaldehydes)
(O--O Bidentates, O--O Ligand can also contain nonbinding N, O, S,
or Tridentates, O--O Tetradentates) P atoms. O Valence Stabilizer
#23: RR'--N--CH(--OH)--NR''--C(.dbd.O)--NR'''R'''', where
N-(Aminomethylol)ureas [N- R, R', R'', R''', and R'''' represent H,
NH.sub.2 or (Aminohydroxymethyl)ureas], Bis[N- any organic
functional group wherein the (aminomethylol)ureas], and Poly[N-
number of carbon atoms ranges from 0 to 40, (aminomethylol)ureas]
(O--O Bidentates, optionally having halogen or polarizing or O--O
Tridentates, O--O Tetradentates) water-insolubilizing/solubilizing
groups attached. Ligand can also contain nonbinding N, O, S, or P
atoms. O Valence Stabilizer #24:
RR'--N--C(.dbd.O)--C(.dbd.O)--N--R''R''', where R, R', Oxamides,
Bis(oxamides), and R'', and R''' represent H, NH.sub.2 or any
organic Poly(oxamides) (O--O Bidentates, O--O functional group
wherein the number of carbon Tridentates, O--O Tetradentates) atoms
ranges from 0 to 40, optionally having halogen or polarizing or
water- insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. O Valence Stabilizer #25:
--C(--OH).dbd.C(--OH)--, where the two carbon atoms Squaric Acids
and derivatives thereof (O--O supporting the hydroxy groups are
included Bidentates) within a cyclic hydrocarbon moiety, optionally
having halogen or polarizing or water- insolubilizing/solubilizing
groups attached. Ligand can also contain nonbinding N, O, S, or P
atoms. O Valence Stabilizer #26:
(R--O--)(O.dbd.)C--R'--C(.dbd.O)(--O--R''), where R, R',
Dicarboxylic Acids, Bis(dicarboxylic and R'' represent H, NH.sub.2
or any organic acids), Poly(dicarboxylic acids), and functional
group wherein the number of carbon derivatives thereof (O--O
Bidentates and atoms ranges from 0 to 40, optionally having O--O
Tetradentates) halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. O Valence Stabilizer #27:
R--O--C(.dbd.O)--O--R', where R, and R' represent H, Carbonates and
Bis(carbonates) (O--O NH.sub.2 or any organic functional group
wherein Bidentates and O--O Tetradentates) the number of carbon
atoms ranges from 0 to 40, optionally having halogen or polarizing
or water-insolubilizing/solubilizing groups attached. Ligand can
also contain nonbinding N, O, S, or P atoms. O Valence Stabilizer
#28: RR'N.sup.+.dbd.C(OH)(OH), where R and R' represent Carbamates,
Bis(carbamates), and H, OH, SH, OR'' (R'' = C.sub.1-C.sub.30 alkyl
or aryl), Poly(carbamates) (including N- SR'' (R'' =
C.sub.1-C.sub.30 alkyl or aryl), NH.sub.2 or any hydroxycarbamates
and N- organic functional group wherein the number of
mercaptocarbamates) (O--O Bidentates, carbon atoms ranges from 0 to
40, optionally O--O Tridentates, and O--O Tetradentates) having
halogen or polarizing or water- insolubilizing/solubilizing groups
attached. Ligand can also contain nonbinding N, O, S, or P atoms. O
Valence Stabilizer #29: RR'N--NR''--C(.dbd.O)(OH), where R and R'
Carbazates (carbazides), Bis(carbazates), represent H, NH.sub.2 or
any organic functional and Poly(carbazates) (O--O Bidentates, O--O
group wherein the number of carbon atoms Tridentates, and O--O
Tetradentates; or ranges from 0 to 40, optionally having halogen
possibly N--O Bidentates, N--O Tridentates, or polarizing or water-
and N--O Tetradentates) insolubilizing/solubilizing groups
attached. Ligand can also contain nonbinding N, O, S, or P atoms. O
Valence Stabilizer #30: RN.dbd.C(OH)(OH), where R represents H,
NH.sub.2 or Carbimates, Bis(carbimates), and any organic functional
group wherein the Poly(carbimates) (O--O Bidentates, O--O number of
carbon atoms ranges from 0 to 40, Tridentates, and O--O
Tetradentates) optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. O Valence Stabilizer #31:
(O.dbd.)As(--O--R)(--O--R')(--O--R''), where R, R', and Arsonic
Acids, Bis(arsonic acids), R'' represent H, NH.sub.2 or any organic
functional Poly(arsonic acids), and derivatives thereof group
wherein the number of carbon atoms (O--O Bidentates, O--O
Tridentates, O--O ranges from 0 to 40, optionally having halogen
Tetradentates) or polarizing or water- insolubilizing/solubilizing
groups attached. Ligand can also contain nonbinding N, O, S, or P
atoms. O Valence Stabilizer #32: R--O--C(--O--R'')--O--R', where R,
R', and R'' Alkyl- and Aryl- Borates and Bis(borates) represent H,
NH.sub.2 or any organic functional (O--O Bidentates and O--O
Tetradentates) group wherein the number of carbon atoms ranges from
0 to 40, optionally having halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. O Valence Stabilizer #33:
R--C(--O--R'')--O--R', where R, R', and R'' Alkyl- and Aryl-
Boronates and represent H, NH.sub.2 or any organic functional
Bis(boronates) (O--O Bidentates and O--O group wherein the number
of carbon atoms Tetradentates) ranges from 0 to 40, optionally
having halogen or polarizing or water- insolubilizing/solubilizing
groups attached. Ligand can also contain nonbinding N, O, S, or P
atoms. O Valence Stabilizer #34: RR'R''P.dbd.O for phosphine
P-oxides, and Phosphine P-oxides and Amino-substituted
(RR'N)(R''R'''N)(R''''R'''''N)P.dbd.O for amino- Phosphine oxides
(0 Monodentates) substituted phosphine oxides, where R, R', R'',
R''', R'''', and R''''' represent H, Cl, Br, NH.sub.2 or any
organic functional group wherein the number of carbon atoms ranges
from 0 to 40, optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. (Rs are
typically aromatic or heterocyclic for phosphine P-oxides.) Ligand
can also contain nonbinding N, O, S, or P atoms. O Valence
Stabilizer #35: RR'R''As.dbd.O for arsine As-oxides, and Arsine
As-oxides and Amino-substituted
(RR'N)(R''R'''N)(R''''R'''''N)As.dbd.O for amino- Arsine oxides (O
Monodentates) substituted arsine oxides, where R, R',
R'', R''', R'''', and R''''' represent H, Cl, Br, NH.sub.2 or any
organic functional group wherein the number of carbon atoms ranges
from 0 to 40, optionally having halogen or polarizing or water-
insolubilizing/solubilizing groups attached. (Rs are typically
aromatic or heterocyclic for arsine As-oxides.) Ligand can also
contain nonbinding N, O, S, or P atoms. O Valence Stabilizer #36:
Cyanates bound directly to the high valence Cyanate ligands (O
Monodentates) metal ion. N--S Valence Stabilizer #1:
RC(.dbd.NH)SR', where R and R' represent H or Thioimidates,
Dithioimidates, any organic functional group wherein the
Polythioimidates, and Derivatives of number of carbon atoms ranges
from 0 to 40, Thioimidic Acid (N--S Bidentates and N--S optionally
having halogen or polarizing or Tetradentates)
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--S Valence Stabilizer #2:
RR'--N--C(.dbd.NH)--NR''--CS--NR'''R'''' for Thioguanylureas,
Guanidinothioureas, thioguanylureas, and
RR'--N--C(.dbd.NH)--NR''--NH-- Bis(thioguanylureas), CS--NR'''R''''
for guanidinothioureas, where R, Bis(guanidinothioureas), R', R'',
R''', and R'''' represent H, NH.sub.2, or any
Poly(thioguanylureas), and organic functional group wherein the
number of Poly(guanidinothioureas) (N--S Bidentates carbon atoms
ranges from 0 to 40, optionally and N--S Tetradentates) having
halogen or polarizing or water- insolubilizing/solubilizing groups
attached. Ligand can also contain nonbinding N, O, S, or P atoms.
N--S Valence Stabilizer #3: RR'--N--C(.dbd.NH)--NR''--CS--R''' for
N- Amidinothioamides, Guanidinothioamides, amidinothioamides, or
RR'--N--C(.dbd.NH)-- Bis(amidinothioamides),
CR''R'''--CS--N--R''''R''''' for 2- Bis(guanidinothioamides),
amidinothioacetamides, and RR'--N--C(.dbd.NH)--
Poly(amidinothioamides), and NR''--NH--CS--R''' for
guanidinothioamides, Poly(guanidinothioamides) (including both
where R, R', R'', R''', R'''', and R''''' represent
N-amidinothioamides and 2- H, NH.sub.2, or any organic functional
group amidinothioacetamides) (N--S Bidentates wherein the number of
carbon atoms ranges and N--S Tetradentates) from 0 to 40,
optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--S Valence Stabilizer #4:
R--C(.dbd.NH)--NR'--CS--R'', where R, R', and R'',
Imidoylthioamides, represent H or any organic functional group
Bis(imidoylthioamides), and wherein the number of carbon atoms
ranges Poly(imidoylthioamides) (N--S Bidentates from 0 to 40,
optionally having halogen or and N--S Tetradentates) polarizing or
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--S Valence Stabilizer #5:
RR'NCSNR''R''', where R, R', R'', and R''' Thioureas,
Bis(thioureas), and represent H, NH.sub.2, or any organic
functional Poly(thioureas), including Thiourylene group wherein the
number of carbon atoms Complexes (N--S Bidentates, N--S ranges from
0 to 40, optionally having halogen Tridentates, and N--S
Tetradentates) or polarizing or water- insolubilizing/solubilizing
groups attached. Ligand can also contain nonbinding N, O, S, or P
atoms. N--S Valence Stabilizer #6: RCSNR'R'', where R, R', and R''
represent H, Thiocarboxamides, Bis(thiocarboxamides), NH.sub.2, or
any organic functional group wherein and Poly(thiocarboxamides)
(N--S the number of carbon atoms ranges from 0 to Bidentates, N--S
Tridentates, and N--S 40, optionally having halogen or polarizing
or Tetradentates) water-insolubilizing/solubilizing groups
attached. Ligand can also contain nonbinding N, O, S, or P atoms.
N--S Valence Stabilizer #7: RR'--N--S(.dbd.NH)--N--R''R''', where
R, R', R'', and Imidosulfurous Diamides and R''' represent H or any
organic functional group Bis(imidosulfurous diamides) (N--S wherein
the number of carbon atoms ranges Bidentates, N--S Tridentates, and
N--S from 0 to 40, optionally having halogen or Tetradentates)
polarizing or water-insolubilizing/solubilizing groups attached.
Ligand can also contain nonbinding N, O, S, or P atoms. N--S
Valence Stabilizer #8: R--N.dbd.S.dbd.N--R', where R and R'
represent H or Sulfurdiimines, Bis(sulfurdiimines), and any organic
functional group wherein the Poly(sulfurdiimines) (N--S Bidentates,
N--S number of carbon atoms ranges from 0 to 40, Tridentates, and
N--S Tetradentates) optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--S Valence Stabilizer #9:
(NH.dbd.)PR(OR')(SR'') for phosphonimidothioic Phosphonimidothioic
Acid, acid and (NH.dbd.)PR(SR')(SR'') for Phosphonimidodithioic
Acid, phosphonimidodithioic acid, where R, R', and
Bis(Phosphonimidothioic acid); R'' represent H or any organic
functional group Bis(Phosphonimidodithioic acid), and wherein the
number of carbon atoms ranges derivatives thereof (N--S Bidentates,
N--S from 0 to 40, optionally having halogen or Tetradentates)
polarizing or water-insolubilizing/solubilizing groups attached.
Ligand can also contain nonbinding N, O, S, or P atoms. N--S
Valence Stabilizer #10: (S.dbd.)PR(--NR'R'')(--NR'''R''''), where
R, R', R'', Phosphonothioic Diamides, R''', and R'''' represent H
or any organic Bis(phosphonothioic diamides), and functional group
wherein the number of carbon Poly(phosphonothioic diamides) (N--S
atoms ranges from 0 to 40, optionally having Bidentates and N--S
Tetradentates) halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--S Valence Stabilizer
#11: (S.dbd.)PR(--NR'R'')(--OR''') or (O.dbd.)PR(--NR'R'')
Phosphonamidothioic Acid, (--SR''') for phosphonamidothioic acid,
(S.dbd.)PR Phosphonamidimidodithioic Acid, (--NR'R'')(--SR''') for
phosphonamidimidodithioic Bis(phosphonamidothioic acid), acid,
where R, R', R'', and R''' represent H or
Bis(phosphonamidimidodithioic acid), any organic functional group
wherein the poly(phosphonamidothioic acid), and number of carbon
atoms ranges from 0 to 40, poly(phosphonamidimidodithioic acid),
and optionally having halogen or polarizing or derivatives thereof
(N--S Bidentates and water-insolubilizing/solubilizing groups N--S
Tetradentates) attached. Ligand can also contain nonbinding N, O,
S, or P atoms. N--S Valence Stabilizer #12:
R--C(.dbd.S)--CR'.dbd.CR''--NHR''', where R, R', R'',
Beta-Aminothiones (N-Substituted 3- and R''' represent H, or any
organic functional amino-2-propenethioaldehydes), Bis(beta- group
wherein the number of carbon atoms aminothiones), and Poly(beta-
ranges from 0 to 40, optionally having halogen aminothiones) (N--S
Bidentates and N--S or polarizing or water- Tetradentates)
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--S Valence Stabilizer
#13: RR'--N--C(.dbd.S)--CR.dbd.C(--NHR''')R'''' for 3-
3-Aminothioacrylamides (3-Amino-2- aminothioacrylamides, and
RR'--N--C(.dbd.S)-- thiopropenamides), 3,3-
CR''.dbd.C(--NHR''')(--NR''''R''''') for 3,3-
Diaminothioacrylamides, Bis(3- diaminothioacrylamides, where R, R',
R'', R''', aminothioacrylamides), Bis(3,3- R'''', R''''' represent
H, NH.sub.2, or any organic diaminoacrylamides), Poly(3- functional
group wherein the number of carbon aminothioacrylamides), and
Poly(3,3- atoms ranges from 0 to 40, optionally having
diaminothioacrylamides) (N--S Bidentates halogen or polarizing or
water- and N--S Tetradentates) insolubilizing/solubilizing groups
attached. Ligand can also contain nonbinding N, O, S, or P atoms.
N--S Valence Stabilizer #14:
R--O--C(.dbd.S)--CR'.dbd.C(--NHR'')R''' or R--S--C(.dbd.S)--
3-Aminothioacrylic Acids (3-Amino-2- CR'.dbd.C(--NHR'')R''' for
3-aminothioacrylic thiopropenoic acids),3-Mercapto-3- acids, and
R--O--C(.dbd.S)--CR'.dbd.C(--NHR'')(--S--R''') aminothioacrylic
acids, Bis(3- or R--S--C(.dbd.S)--CR'.dbd.C(--NHR'')(--S--R''') for
3- aminothioacrylic acids), Bis(3-Hydroxy-3-
mercapto-3-aminothioacrylic acids, where R, aminothioacrylic
acids), Poly(3- R', R'', and R''' represent H, NH.sub.2, or any
aminothioacrylic acids), and Poly(3- organic functional group
wherein the number of Hydroxy-3-aminothioacrylic acids), and carbon
atoms ranges from 0 to 40, optionally derivatives thereof (N--S
Bidentates and having halogen or polarizing or water- N--S
Tetradentates) insolubilizing/solubilizing groups attached. Ligand
can also contain nonbinding N, O, S, or P atoms. N--S Valence
Stabilizer #15: R--C(.dbd.S)--N.dbd.CHR', where R' represents an
N-Thioacyl Benzylidenimines, Bis(N- aromatic derivative (i.e.
--C.sub.6H.sub.5), and R represent thioacyl benzylidenirnines), and
Poly(N- H, NH.sub.2, or any organic functional group thioacyl
benzylidenimines) (N--S Bidentates wherein the number of carbon
atoms ranges and N--S Tetradentates) from 0 to 40, optionally
having halogen or polarizing or water-insolubilizing/solubilizing
groups attached. Ligand can also contain nonbinding N, O, S, or P
atoms. N--S Valence Stabilizer #16: R--C(.dbd.S)--C(.dbd.NOH)--R',
where R and R' Thiocarbonyl oximes, Bis(thiocarbonyl represent H,
NH.sub.2, or any organic functional oximes), and Poly(thiocarbonyl
oximes) group wherein the number of carbon atoms (N--S Bidentates,
N--S Tridentates, and N--S ranges from 0 to 40, optionally having
halogen Tetradentates) or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--S Valence Stabilizer
#17: R--CH(--SH)C(.dbd.NOH)--R', where R, R', and R'' Mercapto
oximes, Bis(mercapto oximes), represent H, NH.sub.2, or any organic
functional and Poly(mercapto oximes) (including 2- group wherein
the number of carbon atoms sulfur heterocyclic oximes) (N--S ranges
from 0 to 40, optionally having halogen Bidentates, N--S
Tridentates, N--S or polarizing or water- Tetradentates, and N--S
Hexadentates) insolubilizing/solubilizing groups attached. Ligand
can also contain nonbinding N, O, S, or P atoms. N--S Valence
Stabilizer #18: o-(O.sub.2N--)(HS--)Ar, where Ar represents an
2-Nitrothiophenols (2-nitrobenzenethiols) aromatic group or
heterocyclic wherein the (N--S Bidentates) number of carbon atoms
ranges from 6 to 40, optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--S Valence Stabilizer
#19: o-(NC--(CH.sub.2).sub.0-1)(HS--)Ar, where Ar represents
2--Nitrilothiophenols (N--S Bidentates) an aromatic group or
heterocyclic wherein the number of carbon atoms ranges from 6 to
40, optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--S Valence Stabilizer
#20: R--C(.dbd.S)--NHNR'R'', where R, R', and R'' Thiohydrazides,
Bis(thiohydrazides), and represent H or any organic functional
group Poly(thiohydrazides) (N--S Bidentates and wherein the number
of carbon
atoms ranges N--S Tetradentates) from 0 to 40, optionally having
halogen or polarizing or water-insolubilizing/solubilizing groups
attached. Ligand can also contain nonbinding N, O, S, or P atoms.
N--S Valence Stabilizer #21: RR'--N--C(.dbd.S)--NHNR''R''', where
R, R', and R'' Thiosemicarbazides, represent H or any organic
functional group Bis(thiosemicarbazides), and wherein the number of
carbon atoms ranges Poly(thiosemicarbazides) (N--S Bidentates, from
0 to 40, optionally having halogen or N--S Tetradentates, and N--S
Hexadentates) polarizing or water-insolubilizing/solubilizing
groups attached. Ligand can also contain nonbinding N, O, S, or P
atoms. N--S Valence Stabilizer #22: Macrocyclic ligands containing
five, seven, or Five-, Seven-, or Nine-Membered nine binding sites
composed of nitrogen and Macrocyclics, Macrobicyclics, and sulfur
to valence stabilize the central metal ion. Macropolycyclics
(including Catapinands, Can include other hydrocarbon or ring
systems Cryptands, Cyclidenes, and Sepulchrates) bound to this
macrocyclic ligand, but they do wherein all Binding Sites are
composed of not coordinate with the stabilized, high valence
Nitrogen (usually amine or irnine groups) metal ion. This ligand
and/or attached, or Sulfur (usually thiols, mercaptans, or
uncoordinating hydrocarbons/rings may or may thiocarbonyls) and are
not contained in not have halogen or polarizing or water- Component
Heterocyclic Rings (N--S insolubilizing/solubilizing groups
attached. Tridentates, N--S Tetradentates, and N--S Hexadentates)
N--S Valence Stabilizer #23: Macrocyclic ligands containing a total
of five or Five-, or Seven-Membered Macrocyclics, seven
heterocyclic rings containing nitrogen or Macrobicyclics, and
Macropolycyclics sulfur binding sites. Can include other (including
Catapinands, Cryptands, hydrocarbon/ring systems bound to this
Cyclidenes, and Sepulchrates) wherein all macrocyclic ligand, but
they do not coordinate Binding Sites are composed of Nitrogen or
with the stabilized, high valence metal ion. Sulfur and are
contained in Component This ligand and/or attached, uncoordinating
Heterocyclic Rings (N--S Tridentates, N--S hydrocarbon/rings may or
may not have Tetradentates, or N--S Hexadentates) halogen or
polarizing or water-insolubilizing groups attached. N--S Valence
Stabilizer #24: Macrocyclic ligands containing at least one Five-,
Seven-, or Nine-Membered heterocyclic ring. These heterocyclic
rings Macrocyclics, Macrobicyclics, and provide nitrogen or sulfur
binding sites to Macropolycyclics (including Catapinands, valence
stabilize the central metal ion. Other Cryptands, Cyclidenes, and
Sepulchrates) amine, imine, thiol, mercapto, or thiocarbonyl
wherein all Binding Sites are composed of binding sites can also be
included in the Nitrogen or Sulfur and are contained in a
macrocyclic ligand, so long as the total number Combination of
Heterocyclic Rings and of binding sites is five, seven, or nine.
Can Amine, Imine, Thiol, Mercapto, or include other
hydrocarbon/ring systems bound Thiocarbonyl Groups (N--S
Tridentates, to this macrocyclic ligand, but they do not N--S
Tetradentates, or N--S Hexadentates) coordinate with the
stabilized, high valence metal ion. This ligand and/or attached,
uncoordinating hydrocarbon/rings may or may not have halogen or
polarizing or water- insolubilizing groups attached. N--O Valence
Stabilizer #1: RC(.dbd.NH)OR', where R and R' represent H or
Imidates, Diimidates, Polyimidates, and any organic functional
group wherein the Derivatives of Imidic Acid (N--O Bidentates
number of carbon atoms ranges from 0 to 40, and N--O Tetradentates)
optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--O Valence Stabilizer #2:
RR'NC(.dbd.NH)OR'', where R, R', and R'' Pseudoureas,
bis(pseudoureas), and represent H, NH.sub.2, or any organic
functional poly(pseudoureas) (N--O Bidentates and group wherein the
number of carbon atoms N--O Tetradentates) ranges from 0 to 40,
optionally having halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--O Valence Stabilizer #3:
RR'NC(.dbd.NH)CR''R'''(CO)OR'''', where R, R', 2-Amidinoacetates,
Bis(2-amidinoacetates), R'', R''', and R'''' represent H, NH.sub.2,
or any and Poly(2-amidinoacetates) (N--O organic functional group
wherein the number of Bidentates and N--O Tetradentates) carbon
atoms ranges from 0 to 40, optionally having halogen or polarizing
or water- insolubilizing/solubilizing groups attached. Ligand can
also contain nonbinding N, O, S, or P atoms. N--O Valence
Stabilizer #4: RR'NCONR''R''', where R, R', R'', and R''' Ureas,
Bis(ureas), and Poly(ureas), represent H, NH.sub.2, or any organic
functional including Urylene Complexes (N--O group wherein the
number of carbon atoms Bidentates, N--O Tridentates, and N--O
ranges from 0 to 40, optionally having halogen Tetradentates) or
polarizing or water- insolubilizing/solubilizing groups attached.
Ligand can also contain nonbinding N, O, S, or P atoms. N--O
Valence Stabilizer #5: (NH.dbd.)PR(OR')(OR''), where R, R', and R''
Phosphonimidic Acid, Bis(phosphonimidic represent H, NH.sub.2, or
any organic functional acid), Poly(phosphonirnidic acid), and group
wherein the number of carbon atoms derivatives thereof (N--O
Bidentates and ranges from 0 to 40, optionally having halogen N--O
Tetradentates) or polarizing or water- insolubilizing/solubilizing
groups attached. Ligand can also contain nonbinding N, O, S, or P
atoms. N--O Valence Stabilizer #6: (O.dbd.)PR(--NR'R'')(--OR''')
for phosphonamidic Phosphonamidic Acid, Phosphonic acid and
(O.dbd.)PR(--NR'R'')(--NR'''R'''') for Diamide, Bis(Phosphonamidic
Acid), phosphonic diamide, where R, R', R'', R''', and
Bis(Phosphonic Diamide), R'''' represent H, NH.sub.2, or any
organic functional Poly(phosphonamidic acid), group wherein the
number of carbon atoms poly(phosphonic diamide), and derivatives
ranges from 0 to 40, optionally having halogen thereof (N--O
Bidentates and N--O or polarizing or water- Tetradentates)
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--O Valence Stabilizer #7:
R--C(.dbd.O)--CR'.dbd.C(--NHR'')R''', where R, R', R'',
Beta-Ketoamines (N-Substituted 3-amino- and R''' represent H, or
any organic functional 2-propenals), Bis(beta-ketoamines), and
group wherein the number of carbon atoms Poly(beta-ketoamines)
(N--O Bidentates and ranges from 0 to 40, optionally having halogen
N--O Tetradentates) or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--O Valence Stabilizer #8:
RR'--N--C(.dbd.O)--CR''.dbd.C(--NHR''')R'''' for 3-
3-Aminoacrylamides (3-Amino-2- aminoacrylamides, and
RR'--N--C(.dbd.O)--CR''.dbd.C propenamides),
3,3-Diaminoacrylamides, (--NHR''')(--NR''''R''''') for 3,3-
Bis(3-aminoacrylamides), Bis(3,3- diaminoacrylamides, where R, R',
R'', R''', R'''', diaminoacrylamides), Poly(3- and R''''' represent
H, NH.sub.2, or any organic aminoacrylamides), and Poly(3,3-
functional group wherein the number of carbon diaminoacrylamides)
(N--O Bidentates and atoms ranges from 0 to 40, optionally having
N--O Tetradentates) halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--O Valence Stabilizer #9:
R--O--C(.dbd.O)--CR'.dbd.C(--NHR'')R''' for 3- 3-Aminoacrylic Acids
(3-Amino-2- aminoacrylic acids, and R--O--C(.dbd.O)--CR'C propenoic
acids), 3-Hydroxy-3- (--NHR'')(--O--R''') for
3-hydroxy-3-aminoacrylic arninoacrylic acids, Bis(3-aminoacrylic
acids, where R, R', R'', and R''' represent H, acids),
Bis(3-Hydroxy-3-aminoacrylic NH.sub.2, or any organic functional
group wherein acids), Poly(3-aminoacrylic acids), and the number of
carbon atoms ranges from 0 to Poly(3-Hydroxy-3-aminoacrylic acids),
and 40, optionally having halogen or polarizing or derivatives
thereof (N--O Bidentates and water-insolubilizing/solubilizing
groups N--O Tetradentates) attached. Ligand can also contain
nonbinding N, O, S, or P atoms. N--O Valence Stabilizer #10:
R--C(.dbd.O)--N.dbd.CHR', where R' represents an N-Acyl
Benzylidenimines, Bis(N-acyl aromatic derivative (i.e.
--C.sub.6H.sub.5), and R represent benzylidenimines), and
Poly(N-acyl H, NH.sub.2, or any organic functional group
benzylidenimines) (N--O Bidentates and wherein the number of carbon
atoms ranges N--O Tetradentates) from 0 to 40, optionally having
halogen or polarizing or water-insolubilizing/solubilizing groups
attached. Ligand can also contain nonbinding N, O, S, or P atoms.
N--O Valence Stabilizer #11: o-(O.sub.2N--)(RR'N--)Ar, where Ar
represents an 2-Nitroanilines (N--O Bidentates) aromatic group or
heterocyclic wherein the number of carbon atoms ranges from 6 to
40, and R and R' represent H, NH.sub.2, or alkyl or aryl
hydrocarbon groups wherein the number of carbon atoms range from 0
to 25, optionally having halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. N--O Valence Stabilizer
#12: o-(NC--(CH.sub.2).sub.0-1)(HO--)Ar, where Ar represents
2-Nitrilophenols (N--O Bidentates). an aromatic group or
heterocyclic wherein the Also includes acylcyanamides. number of
carbon atoms ranges from 6 to 40, optionally having halogen or
polarizing or water-insolubilizing/solubilizing groups attached.
Ligand can also contain nonbinding N, O, S, or P atoms. N--O
Valence Stabilizer #13: HetN.sup.+--O.sup.- for amine N-oxides, and
R--N.dbd.N.sup.+ Amine N-Oxides and Diazine N-Oxides
(--O.sup.-)--R' for diazine N-oxides (azoxy compounds), (Azoxy
componds) (N--O Bidentates, N--O where Het represents a
nitrogen-containing Tridentates, and N--O Tetradentates)
heterocyclic derivative wherein the number of carbon atoms ranges
from 4 to 40, and R and R' represent separate or the same aromatic
functionalities, both Het and R,R' optionally having halogen or
polarizing or water- insolubilizing/solubilizing groups attached.
Ligand can also contain nonbinding N, O, S, or P atoms. N--O
Valence Stabilizer #14: R--C(.dbd.O)--NHNR'R'', where R, R', and
R'' Hydrazides, Bis(hydrazides), and represent H or any organic
functional group Poly(hydrazides) (N--O Bidentates and N--O wherein
the number of carbon atoms ranges Tetradentates) from 0 to 40,
optionally having halogen or polarizing or
water-insolubilizing/solubilizing
groups attached. Ligand can also contain nonbinding N, O, S, or P
atoms. N--O Valence Stabilizer #15: RR'--N--C(.dbd.O)--NHNR''R''',
where R, R', and Semicarbazides, Bis(semicarbazides), and R''
represent H or any organic functional group Poly(semicarbazides)
(N--O Bidentates, wherein the number of carbon atoms ranges N--O
Tetradentates, and N--O Hexadentates) from 0 to 40, optionally
having halogen or polarizing or water-insolubilizing/solubilizing
groups attached. Ligand can also contain nonbinding N, O, S, or P
atoms. N--O Valence Stabilizer #16: Macrocyclic ligands containing
five, seven, or Five-, Seven-, or Nine-Membered nine binding sites
composed of nitrogen and Macrocyclics, Macrobicyclics, and oxygen
to valence stabilize the central metal Macropolycyclics (including
Catapinands, ion. Can include other hydrocarbon or ring Cryptands,
Cyclidenes, and Sepulchrates) systems bound to this macrocyclic
ligand, but wherein all Binding Sites are composed of they do not
coordinate with the stabilized, high Nitrogen (usually amine or
imine groups) valence metal ion. This ligand and/or attached, or
Oxygen (usually hydroxy, carboxy, or uncoordinating
hydrocarbons/rings may or may carbonyl groups) and are not
contained in not have halogen or polarizing or water- Component
Heterocyclic Rings (N--O insolubilizing/solubilizing groups
attached. Tridentates, N--O Tetradentates, and N--O Hexadentates)
N--O Valence Stabilizer #17: Macrocyclic ligands containing a total
of five or Five-, or Seven-Membered Macrocyclics, seven
heterocyclic rings containing nitrogen or Macrobicyclics, and
Macropolycyclics oxygen binding sites. Can include other (including
Catapinands, Cryptands, hydrocarbon/ring systems bound to this
Cyclidenes, and Sepulchrates) wherein all macrocyclic ligand, but
they do not coordinate Binding Sites are composed of Nitrogen or
with the stabilized, high valence metal ion. Oxygen and are
contained in Component This ligand and/or attached, uncoordinating
Heterocyclic Rings (N--O Tridentates, N--O hydrocarbon/rings may or
may not have Tetradentates, or N--O Hexadentates) halogen or
polarizing or water-insolubilizing groups attached. N--O Valence
Stabilizer #18: Macrocyclic ligands containing at least one Five-,
Seven-, or Nine-Membered heterocyclic ring. These heterocyclic
rings Macrocyclics, Macrobicyclics, and provide nitrogen or oxygen
binding sites to Macropolycyclics (including Catapinands, valence
stabilize the central metal ion. Other Cryptands, Cyclidenes, and
Scpulchrates) amine, imine, hydroxy, carboxy, or carbonyl wherein
all Binding Sites are composed of binding sites can also be
included in the Nitrogen or Oxygen and are contained in a
macrocyclic ligand, so long as the total number Combination of
Heterocyclic Rings and of binding sites is five, seven, or nine.
Can Amine, Imine, Hydroxy, Carboxy, or include other
hydrocarbon/ring systems bound Carbonyl Groups (N--O Tridentates,
N--O to this macrocyclic ligand, but they do not Tetradentates, or
N--O Hexadentates) coordinate with the stabilized, high valence
metal ion. This ligand and/or attached, uncoordinating
hydrocarbon/rings may or may not have halogen or polarizing or
water- insolubilizing groups attached. S--O Valence Stabilizer #1:
RR'--N--C(.dbd.S)--NR''--C(.dbd.O)--NR'''R'''' for Thiobiurets
(Thioimidodicarbonic thiobiurets, and
RR'--N--C(.dbd.S)--NR''--NH--C(.dbd.O)-- Diamides), Thioisobiurets,
Thiobiureas, NR'''R'''' for thiobiureas, where R, R', R'', R''',
Thiotriurets, Thiotriureas, Bis(thiobiurets), and R'''' represent
H, NH.sub.2, or any organic Bis(thioisobiurets), Bis(thiobiureas),
functional group wherein the number of carbon Poly(thiobiurets),
Poly(thioisobiurets), atoms ranges from 0 to 40, optionally having
Poly(thiobiureas) (S--O Bidentates, S--O halogen or polarizing or
water- Tridentates, S--O Tetradentates), and 3-
insolubilizing/solubilizing groups attached. formamidino
thiocarbamides Ligand can also contain nonbinding N, O, S, or P
atoms. S--O Valence Stabilizer #2:
RR'--N--C(.dbd.S)--NR''--C(.dbd.O)--R''' for acyl- and
Acylthioureas, Aroylthioureas, aroylthioureas, and
RR'--N--C(.dbd.O)--NR''--C(.dbd.S)-- Thioacylureas, Thioaroylureas,
R''' for thioacyl- and thioaroylureas, where R, Bis(acylthioureas),
Bis(aroylthioureas), R', R'', and R''' represent H, NH.sub.2, or
any Bis(thioacylureas), Bis(thioaroylureas), organic functional
group wherein the number of Poly(thioacylthioureas), carbon atoms
ranges from 0 to 40, optionally Poly(thioaroylthioureas), having
halogen or polarizing or water- Poly(thioacylureas), and
insolubilizing/solubilizing groups attached. Poly(thioaroylureas)
(S--O Bidentates, S--O Ligand can also contain nonbinding N, O, S,
or Tridentates, S--O Tetradentates) P atoms. S--O Valence
Stabilizer #3: RC(.dbd.S)--NR'--(.dbd.O)--R'' for
Thioimidodialdehydes, thioimidodialdehydes, and
RC(.dbd.S)--NR'--NH-- Thiohydrazidodialdehydes (thioacyl
C(.dbd.O)--R'' for thiohydrazidodialdehydes hydrazides),
Bis(thioimidodialdehydes), (thioacyl hydrazides), where R, R', and
R'' Bis(thiohydrazidodialdehydes), represent H, NH.sub.2, or any
organic functional Poly(thioimidodialdehydes), and group wherein
the number of carbon atoms Poly(thiohydrazidodialdehydes) (S--O
ranges from 0 to 40, optionally having halogen Bidentates, S--O
Tridentates, S--O or polarizing or water- Tetradentates)
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S--O Valence Stabilizer #4:
R--O--C(.dbd.S)--NR'--C(.dbd.O)--O--R'' or R--S--C(.dbd.S)--
Thioimidodicarbonic acids, NR'--C(.dbd.O)--S--R'' for
thioimidodicarbonic Thiohydrazidodicarbonic acids, acids, and
R--O--C(.dbd.S)--NR'--NH--C(.dbd.O)--O--R'' or
Bis(thioimidodicarbonic acids),
R--S--C(.dbd.S)--NR'--NH--C(.dbd.O)--S--R'' for
Bis(thiohydrazidodicarbonic acids), thiohydrazidodicarbonic acids,
where R, R', Poly(thioimidodicarbonic acids), and R'' represent H,
NH.sub.2, or any organic Poly(thiohydrazidodicarbonic acids) and
functional group wherein the number of carbon derivatives thereof
(S--O Bidentates, S--O atoms ranges from 0 to 40, optionally having
Tridentates, S--O Tetradentates) halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S--O Valence Stabilizer #5:
R--C(.dbd.S)--C(.dbd.O)--R' where R and R' represent
1,2-Monothioketones (Monothiolenes, H, NH.sub.2, or any organic
functional group Monothio-alpha-ketonates), 1,2,3- wherein the
number of carbon atoms ranges Monothioketones, 1,2,3-Dithioketones,
from 0 to 40, optionally having halogen or Monothiotropolonates,
ortho- polarizing or water-insolubilizing/solubilizing
Monothioquinones, Bis(1,2- groups attached. Ligand can also contain
Monothioketones), and Poly(1,2- nonbinding N, O, S, or P atoms.
Monothioketones) (S--O Bidentates, S--O Tridentates, S--O
Tetradentates) S--O Valence Stabilizer #6:
RR'--N--C(.dbd.S)--S--S--C(.dbd.O)--N--R''R''' for
Trithioperoxydicarbonic Diamides, trithioperoxydicarbonic diamides,
and RR'--N-- Dithioperoxydicarbonic Diamides,
C(.dbd.O)--S--S--C(.dbd.O)--N--R''R''' for
Bis(trithioperoxydicarbonic diamides), dithioperoxydicarbonic
diamides, where R, R', Bis(dithioperoxydicarbonic diamides), R'',
R''' represent H or any organic functional
poly(trithioperoxydicarbonic diamides) and group wherein the number
of carbon atoms poly(dithioperoxydicarbonic diamides) ranges from 0
to 40, optionally having halogen S--O Bidentates, S--O Tridentates,
S--O or polarizing or water- Tetradentates)
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S--O Valence Stabilizer #7:
R--O--C(.dbd.S)--S--C(.dbd.O)--O--R', where R and R'
Diithiodicarbonic Acids, represent H, NH.sub.2 or any organic
functional Bis(dithiodicarbonic acids), group wherein the number of
carbon atoms Poly(dithiodicarbonic acids), and ranges from 0 to 40,
optionally having halogen derivatives thereof (S--O Bidentates,
S--O or polarizing or water- Tridentates, S--O Tetradentates)
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S--O Valence Stabilizer #8:
R--O--C(.dbd.S)--S--S--C(.dbd.O)--O--R', where R and R'
Trithioperoxydicarbonic Acids, represent H, NH.sub.2 or any organic
functional Bis(trithioperoxydicarbonic acids), group wherein the
number of carbon atoms poly(trithioperoxydicarbonic acids), and
ranges from 0 to 40, optionally having halogen derivatives thereof
(S--O Bidentates, S--O or polarizing or water- Tridentates, S--O
Tetradentates) insolubilizing/solubilizing groups attached. Ligand
can also contain nonbinding N, O, S, or P atoms. S--O Valence
Stabilizer #9:
(RR'--N--)(R''R'''--N--)P(.dbd.S)--S--S--P(.dbd.O)(--N--
Monothioperoxydiphosphoramide, R''''R''''')(--N--R''''''R'''''''),
where R, R', R'', R''', Bis(monothioperoxyphosphoramide), and
R'''', R''''', R'''''', and R''''''' represent H, NH.sub.2 or
Poly(monothioperoxydiphosphoramide) any organic functional group
wherein the S--O Bidentates, S--O Tridentates, number of carbon
atoms ranges from 0 to 40, S--O Tetradentates) optionally having
halogen or polarizing or water-insolubilizing/solubilizing groups
attached. Ligand can also contain nonbinding N, O, S, or P atoms.
S--O Valence Stabilizer #10:
(R--O--)(R'--O--)P(.dbd.S)--S--S--P(.dbd.O)(--O--R'')(--O--
Monothioperoxydiphosphoric Acids, R''');
(R--O--)(R'--S--)P(.dbd.S)--S--S--P(.dbd.O)(--S--R'')
Bis(monothioperoxyphosphoric Acids), (--O--R'''); or
(R--S--)(R'--S--)P(.dbd.S)--S--S--P(.dbd.O)(--S--
Poly(monothioperoxydiphosphoric Acids), R'')(--S--R'''), where R,
R', R'', R''', R'''', R''''', and derivatives thereof (S--O
Bidentates, R'''''', and R''''''' represent H, NH.sub.2 or any S--O
Tridentates, S--O Tetradentates) organic functional group wherein
the number of carbon atoms ranges from 0 to 40, optionally having
halogen or polarizing or water- insolubilizing/solubilizing groups
attached. Ligand can also contain nonbinding N, O, S, or P atoms.
S--O Valence Stabilizer #11:
(R--O--)(R'--)P(.dbd.S)--NH--P(.dbd.O)(--R'')(--O--R''');
Monothioimidodiphosphonic Acids,
(R--S--)(R'--)P(.dbd.S)--NH--P(.dbd.O)(--R'')(--O--R'''); or
Monothiohydrazidodiphosphonic Acids,
(R--S--)(R'--)P(.dbd.S)--NH--P(.dbd.O)(--R'')(--S--R''') for
Bis(monothioimidodiphosphonic Acids), monothioimidodiphosphonic
acids, and --NH-- Bis(monothiohydrazidodiphosphonic NH--
derivatives for Acids), Poly(monothioimidodiphosphonic
monothiohydrazidodiphosphonic acids, where Acid), R, R', R'', and
R''' represent H, NH.sub.2 or any
Poly(monothiohydrazidodiphosphonic organic functional group wherein
the number of Acids), and derivatives thereof (S--O carbon atoms
ranges from 0 to 40, optionally Bidentates, S--O Tridentates, S--O
having halogen or polarizing or water- Tetradentates)
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or
P atoms. S--O Valence Stabilizer #12:
(RR'--N--)(R''--)(.dbd.S)--NH--P(.dbd.O)(--R''')(--N--
Monothioimidodiphosphonamides, R''''R''''') for
Monothiohydrazidodiphosphonamides, monothiolmidodiphosphonamides,
and --NH-- Bis(monothioimidodiphosphonamides), NH-- derivatives for
Bis(monothiohydrazidodiphosphonamides)
monothiohydrazidodiphosphonamides, where
Poly(monothioimidodiphosphonamides), R, R', R'', R''', R'''', and
R''''', represent H, NH.sub.2 and or any organic functional group
wherein the Poly(monothiohydrazidodiphosphonamides) number of
carbon atoms ranges from 0 to 40, (S--O Bidentates, S--O
Tridentates, S--O optionally having halogen or polarizing or
Tetradentates) water-insolubilizing/solubilizing groups attached.
Ligand can also contain nonbinding N, O, S, or P atoms. S--O
Valence Stabilizer #13:
(RR'--N--)(R''--)P(.dbd.S)--S--P(.dbd.O)(--R''')(--N--
Monothiodiphosphonamides, R''''R'''''), or
(RR'--N--)(R''--)P(.dbd.S)--O--P(.dbd.O)
Bis(monothioiphosphonamides), and (--R''')(--N--R''''R'''''), where
R, R', R'', R''', R'''', Poly(monothiodiphosphonamides) (S--O and
R''''' represent H, NH.sub.2 or any organic Bidentates, S--O
Tridentates, S--O functional group wherein the number of carbon
Tetradentates) atoms ranges from 0 to 40, optionally having halogen
or polarizing or water- insolubilizing/solubilizing groups
attached. Ligand can also contain nonbinding N, O, S, or P atoms.
S--O Valence Stabilizer #14:
(R--O--)(R'--)P(.dbd.S)--O--P(.dbd.O)(--R'')(--O--R''');
Monothiodiphosphonic Acids,
(R--O--)(R'--)P(.dbd.S)--S--P(.dbd.O)(--R'')(--O--R'''); (R--S--)
Bis(monothioiphosphonic Acids),
(R'--)P(.dbd.S)--O--P(.dbd.O)(--R'')(--S--R'''); or (R--S--)
Poly(monothiodiphosphonic Acids), and
(R'--)P(.dbd.S)--S--P(.dbd.O)(--R'')(--S--R'''), where R,
derivatives thereof (S--O Bidentates, S--O R', R'', and R'''
represent H, NH.sub.2 or any Tridentates, S--O Tetradentates)
organic functional group wherein the number of carbon atoms ranges
from 0 to 40, optionally having halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, 0, S, or P atoms. S--O Valence Stabilizer
#15: (RR'--N--)(R''--)P(.dbd.S)--S--S--P(.dbd.O)(--R'41 )(--N--
Monothioperoxydiphosphonamide, R''''R'''''), where R, R', R'',
R''', R'''', and R''''' Bis(monothioperoxyphosphonamide), and
represent H, NH.sub.2 or any organic functional
Poly(monothioperoxydiphosphonamide) group wherein the number of
carbon atoms (S--O Bidentates, S--O Tridentates, S--O ranges from 0
to 40, optionally having halogen Tetradentates) or polarizing or
water- insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S--O Valence Stabilizer
#16: (R--O--)(R'--)P(.dbd.S)--S--S--P(.dbd.O)(--R'')(--O--R'''); or
Monothioperoxydiphosphonic Acids,
(R--S--)(R'--)P(.dbd.S)--S--S--P(.dbd.O)(--R'')(--S--R'''),
Bis(monothioperoxyphosphonic Acids), where R, R', R'', and R'''
represent H, NH.sub.2 or Poly(monothioperoxydiphosphonic Acids),
any organic functional group wherein the and derivatives thereof
(S--O Bidentates, number of carbon atoms ranges from 0 to 40, S--O
Tridentates, S--O Tetradentates) optionally having halogen or
polarizing or water-insolubilizing/solubilizing groups attached.
Ligand can also contain nonbinding N, O, S, or P atoms. S--O
Valence Stabilizer #17: (O.dbd.)P(--S--R)(--O--R')(--O--R'') or
(S.dbd.)P(--O--R) Monothiophosphoric Acids (--O--R')(--O--R''),
where R, R', and R'' represent (Phosphorothioic Acids), H, NH.sub.2
or any organic functional group wherein Bis(monothiophosphoric
acids), the number of carbon atoms ranges from 0 to
Poly(monothiophosphoric acids), and 40, optionally having halogen
or polarizing or derivatives thereof (S--O Bidentates, S--O
water-insolubilizing/solubilizing groups Tridentates, S--O
Tetradentates) attached. Ligand can also contain nonbinding N, O,
S, or P atoms. S--O Valence Stabilizer #18:
(O.dbd.)P(--S--S--R)(--O--R')(--O--R''), where R, R',
Phosphoro(dithioperoxoic) Acids, and R'' represent H, NH.sub.2 or
any organic Bis[phosphoro(dithioperoxoic) acids], functional group
wherein the number of carbon Poly[phosphoro(dithioperoxoic) acids],
and atoms ranges from 0 to 40, optionally having derivatives
thereof (S--O Bidentates, S--O halogen or polarizing or water-
Tridentates, S--O Tetradentates) insolubilizing/solubilizing groups
attached. Ligand can also contain nonbinding N, O, S, or P atoms.
S--O Valence Stabilizer #19: (O.dbd.)PR(--S--R')(--O--R'') or
(S.dbd.)PR(--O--R')(--O-- Monothiophosphonic Acids R''), where R,
R', and R'' represent H, NH.sub.2 or (Phosphonothioic Acids), any
organic functional group wherein the Bis(monothiophosphonic Acids),
number of carbon atoms ranges from 0 to 40, Poly(monothiophosphonic
Acids), and optionally having halogen or polarizing or derivatives
thereof (S--O Bidentates, S--O water-insolubilizing/solubilizing
groups Tridentates, S--O Tetradentates) attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S--O Valence Stabilizer
#20: (O.dbd.)PR(--S--S--R')(--O--R''), where R, R', and R''
Phosphono(dithioperoxoic) Acids, represent H, NH.sub.2 or any
organic functional Bis[phosphono(dithioperoxoic) Acids], group
wherein the number of carbon atoms Poly[phosphono(dithioperoxoic)
Acids], ranges from 0 to 40, optionally having halogen and
derivatives thereof (S--O Bidentates, or polarizing or water- S--O
Tridentates, S--O Tetradentates) insolubilizing/solubilizing groups
attached. Ligand can also contain nonbinding N, O, S, or P atoms.
S--O Valence Stabilizer #21:
R--CR'(--OH)--CH.sub.2--C(.dbd.S)--R'', where R, R', and
Beta-Hydroxythioketones, Beta- R'' represent H, NH.sub.2 or any
organic functional Hydroxythioaldehydes, Bis(beta- group wherein
the number of carbon atoms hydroxythioketones), Bis(beta- ranges
from 0 to 40, optionally having halogen hydroxythioaldehydes),
Poly(beta- or polarizing or water- hydroxythioketones), and
Poly(beta- insolubilizing/solubilizing groups attached.
hydroxythioaldehydes) (S--O Bidentates, Ligand can also contain
nonbinding N, O, S, or S--O Tridentates, S--O Tetradentates) P
atoms. S--O Valence Stabilizer #22:
R--CR'(--SH)--CH.sub.2--C(.dbd.O)--R'', where R, R', and
Beta-Mercaptoketones, Beta- R'' represent H, NH.sub.2 or any
organic functional Mercaptoaldehydes, Bis(beta- group wherein the
number of carbon atoms mercaptoketones), Bis(beta- ranges from 0 to
40, optionally having halogen mercaptoaldehydes), Poly(beta- or
polarizing or water- mercaptoketones), and Poly(beta-
insolubilizing/solubilizing groups attached. mercaptoaldehydes)
(S--O Bidentates, S--O Ligand can also contain nonbinding N, O, S,
or Tridentates, S--O Tetradentates) P atoms. S--O Valence
Stabilizer #23: RR'--N--CH(--OH)--NR''--C(.dbd.S)--NR'''R''''',
where N-(Aminomethylol)thioureas [N- R, R', R'', R''', and R''''
represent H, NH.sub.2 or (Aminohydroxymethyl)thioureas], Bis[N- any
organic functional group wherein the (aminomethylol)thioureas], and
Poly[N- number of carbon atoms ranges from 0 to 40,
(aminomethylol)thioureas] (S--O optionally having halogen or
polarizing or Bidentates, S--O Tridentates, S--O
water-insolubilizing/solubilizing groups Tetradentates) attached.
Ligand can also contain nonbinding N, O, S, or P atoms. S--O
Valence Stabilizer #24:
RR'--N--CH(--SH)--NR''--C(.dbd.O)--NR'''R'''', where
N-(Aminomethylthiol)ureas [N- R, R', R'', R''', and R'''' represent
H, NH.sub.2 or (Aminomercaptomethyl)ureas], Bis[N- any organic
functional group wherein the (aminomethylthiol)ureas], and Poly[N-
number of carbon atoms ranges from 0 to 40,
(aminomethylthiol)ureas] (S--O Bidentates, optionally having
halogen or polarizing or S--O Tridentates, S--O Tetradentates)
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S--O Valence Stabilizer
#25: RR'--N--C(.dbd.S)--C(.dbd.O)--N--R''R''', where R, R',
Monothiooxamides, R'', and R''' represent H, NH.sub.2 or any
organic Bis(monothiooxamides), and functional group wherein the
number of carbon Poly(monothiooxamides) (S--O Bidentates, atoms
ranges from 0 to 40, optionally having S--O Tridentates, S--O
Tetradentates) halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S--O Valence Stabilizer
#26: R--CR'(--SH)--CR''R'''--C(.dbd.O)(--O--R''''), where R,
Beta-Mercapto Carboxylic Acids, Bis(Beta- R', R'', R''', and R''''
represent H, NH.sub.2 or any Mercapto Carboxylic Acids), Poly(Beta-
organic functional group wherein the number of Mercapto Carboxylic
Acids), and carbon atoms ranges from 0 to 40, optionally
derivatives thereof (S--O Bidentates, S--O having halogen or
polarizing or water- Tridentates, S--O Tetradentates)
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S--O Valence Stabilizer
#27: R--CR'(--SH)--CR''R'''--C(.dbd.O)(--S--R''''), where R,
Beta-Mercapto Thiocarboxylic Acids, R', R'', R''', and R''''
represent H, NH.sub.2 or any Bis(Beta-Mercapto Thiocarboxylic
Acids), organic functional group wherein the number of
Poly(Beta-Mercapto Thiocarboxylic carbon atoms ranges from 0 to 40,
optionally Acids), and derivatives thereof (S--O having halogen or
polarizing or water- Bidentates, S--O Tridentates, S--O
insolubilizing/solubilizing groups attached. Tetradentates) Ligand
can also contain nonbinding N, O, S, or P atoms. S--O Valence
Stabilizer #28: R--CR'(--OH)--CR''R'''--C(.dbd.O)(--S--R''''),
where R, Beta-Hydroxy Thiocarboxylic Acids, R', R'', R''', and
R'''' represent H, NH.sub.2 or any Bis(Beta-Hydroxy Thiocarboxylic
Acids), organic functional group wherein the number of
Poly(Beta-Hydroxy Thiocarboxylic Acids), carbon atoms ranges from 0
to 40, optionally and derivatives thereof (S--O Bidentates, having
halogen or polarizing or water S--O Tridentates, S--O
Tetradentates) insolubilizing/solubilizing groups attached. Ligand
can also contain nonbinding N, O, S, or P atoms. S--O Valence
Stabilizer #29: R--CR' (--SH)--CR''R'''--C(.dbd.O)(--NH--R''''),
where Beta-Mercapto Carboxamides, Bis(Beta- R, R', R'', R''', and
R'''' represent H, NH or Mercapto Carboxamides), Poly(Beta- any
organic functional group wherein the Mercapto Carboxamides), and
derivatives number of carbon atoms ranges from 0 to 40, thereof
(S--O Bidentates, S--O Tridentates, optionally having halogen
or
polarizing or S--O Tetradentates) water-insolubilizing/solubilizing
groups attached. Ligand can also contain nonbinding N, O, S, or P
atoms. S--O Valence Stabilizer #30: R--S--R'COOH for
S-alkylthiocarboxylic and S-Alkylthiocarboxylic Acids, S-
S-arylthiocarboxylic acids, and HOOCR--S-- Arylthiocarboxylic
Acids, and S,S- R'COOH for S,S-thiobiscarboxylic acids,
thiobiscarboxylic Acids (S--O Bidentates where R and R' represent H
or any organic and S--O Tridentates) functional group wherein the
number of carbon atoms ranges from 0 to 40, optionally having
halogen or polarizing or water- insolubilizing/solubilizing groups
attached. Ligand can also contain nonbinding N, O, S, or P atoms.
S--O Valence Stabilizer #31: R--S--S--R'COOH for
S-alkyldisulfidocarboxylic S-Alkyldisulfidocarboxylic Acids, S- and
S-aryldisulfidocarboxylic acids, and Aryldisulfidocarboxylic Acids,
and S,S'- HOOCR--S--S--R'COOH for S,S'- Disulfidobiscarboxylic
Acids (S--O disulfidobiscarboxylic acids, where R and R' Bidentates
and S--O Tridentates) represent H or any organic functional group
wherein the number of carbon atoms ranges from 0 to 40, optionally
having halogen or polarizing or water-insolubilizing/solubilizing
groups attached. Ligand can also contain nonbinding N, O, S, or P
atoms. S--O Valence Stabilizer #32: R--C(.dbd.O)(--S--R') for
monothiomonocarboxylic Monothiomonocarboxylic Acids, acids, and
(R--S--)(O.dbd.)C--R'--C(.dbd.O)(--S--R'') or Dithiodicarboxylic
Acids, (R--S--)(O.dbd.)C--R'--C(.dbd.O)(--O--R'') for
Bis(monothiomonocarboxylic Acids), dithiodicarboxylic acids, where
R, R', and R'' Bis(dithiodicarboxylic acids), represent H, NH.sub.2
or any organic functional Poly(monothiomonocarboxylic acids), group
wherein the number of carbon atoms Poly(dithiodicarboxylic acids),
and ranges from 0 to 40, optionally having halogen derivatives
thereof (S--O Bidentates and or polarizing or water S--O
Tetradentates) insolubilizing/solubilizing groups attached. Ligand
can also contain nonbinding N, O, S, or P atoms. S--O Valence
Stabilizer #33: R--O--C(.dbd.S)--O--R', where R, and R' represent
H, Monothiocarbonates and NH.sub.2 or any organic functional group
wherein Bis(monothiocarbonates) (S--O Bidentates the number of
carbon atoms ranges from 0 to and S--O Tetradentates) 40,
optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N O, S, or P atoms. S--O Valence Stabilizer #34:
RR'N--NR''--C(.dbd.O)(SH), where R and R' Monothiocarbazates
(Monothiocarbazides), represent H, NH.sub.2 or any organic
functional Bis(monothiocarbazatcs), and group wherein the number of
carbon atoms Poly(monothiocarbazates) (S--O Bidentates, ranges from
0 to 40, optionally having halogen S--O Tridentates, and S--O
Tetradentates; or or polarizing or water- possibly N--S Bidentates,
N--S Tridentates, insolubilizing/solubilizing groups attached. and
N--S Tetradentates) Ligand can also contain nonbinding N, O, S, or
P atoms. S--O Valence Stabilizer #35: R--CH(--SH)--CH(--OH)--R' for
alpha-mercapto Mercapto Alcohols and alcohols,
R--CH(--SH)--Si(--OR').sub.x--R''.sub.3-x for alpha-
Silylmercaptoalcohols, Bis(mercapto silylmercaptoalcohols,
R--CH(--SH)--R'--CH alcohols and silylmercaptoalcohols), and
(--OH)--R'' for beta-mercapto alcohols, and R-- Poly(mercapto
alcohols and CH(--SH)--R'--Si(--OR'').sub.x--R'''.sub.3x for beta-
silylmercaptoalcohols) (S--O Bidentates, silylmercaptoalcohols,
etc., where R, R', R'', S--O Tridentates, S--O Tetradentates) and
R''' represent H, NH.sub.2 or any organic functional group wherein
the number of carbon atoms ranges from 0 to 40, optionally having
halogen or polarizing or water- insolubilizing/solubilizing groups
attached. x = 1-3. Ligand can also contain nonbinding N, O, S, or P
atoms. S--O Valence Stabilizer #36: RN.dbd.C(OH)(SH), where R
represents H, NH.sub.2 or Monothiocarbimates, any organic
functional group wherein the Bis(monothiocarbimates), and number of
carbon atoms ranges from 0 to 40, Poly(monothiocarbimates) (S--O
Bidentates, optionally having halogen or polarizing or S--O
Tridentates, and S--O Tetradentates)
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S--O Valence Stabilizer
#37: R--O--C(--S--R'')--O--R', where R, R', and R'' Alkyl- and
Aryl- Monothioborates and represent H, NH.sub.2 or any organic
functional Bis(monothioborates) (S--O Bidentates and group wherein
the number of carbon atoms S--O Tetradentates) ranges from 0 to 40,
optionally having halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S--O Valence Stabilizer
#38: R--C(--S--R'')--O--R', where R, R', and R'' Alkyl- and Aryl-
Monothioboronates and represent H, NH.sub.2 or any organic
functional Bis(monothioboronates) (S--O Bidentates group wherein
the number of carbon atoms and S--O Tetradentates) ranges from 0 to
40, optionally having halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S--O Valence Stabilizer
#39: (O.dbd.)As(--S--R)(--O--R')(--O--R'') or (S.dbd.)As(--O--
Monothioarsonic Acids (Arsonothioic R)(--O--R')(--O--R''), where R,
R', and R'' Acids), Bis(monothioarsonic acids), represent H,
NH.sub.2 or any organic functional Poly(monothioarsonic acids), and
group wherein the number of carbon atoms derivatives thereof (S--O
Bidentates, S--O ranges from 0 to 40, optionally having halogen
Tridentates, S--O Tetradentates) or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. S--O Valence Stabilizer
#40: Heterocyclic ring(s) containing one or two Heterocyclic Rings
containing One or Two sulfur atoms. In addition, ligand contains
Sulfur Atoms at least one additional additional oxygen-containing
substituents Oxygen Atom Binding Site not in a Ring (usually
hydroxy, carboxy, or carbonyl groups) (S--O Bidentates, S--O
Tridentates, S--O that constitute O binding sites. Can include
Tetradentates, or S--O Hexadentates) other ring systems bound to
the heterocyclic ring or to the O-containing substituent, but they
do not coordinate with the stabilized, high valence metal ion.
Ring(s) can also contain O, N, P, As or Se atoms. This 5-membered
ring(s) and/or attached, uncoordinating rings and/or O- containing
substituent(s) may or may not have halogen or polarizing or water-
insolubilizing/solubilizing groups attached. S--O Valence
Stabilizer #41: Heterocyclic ring(s) containing one or two
Heterocyclic Rings containing One or Two oxygen atoms. In addition,
ligand contains Oxygen Atoms at least one additional additional
sulfur-containing substituents Sulfur Atom Binding Site not in a
Ring (usually thio, mercapto, or thiocarbonyl groups) S--O
Bidentates, S--O Tridentates, S--O that constitute S binding sites.
Can include Tetradentates, or S--O Hexadentates) other ring systems
bound to the heterocyclic ring or to the S-containing substituent,
but they do not coordinate with the stabilized, high valence metal
ion. Ring(s) can also contain O, N, P, As or Se atoms. This
5-membered ring(s) and/or attached, uncoordinating rings and/or 5-
containing substituent(s) may or may not have halogen or polarizing
or water- insolubilizing/solubilizing groups attached. S--O Valence
Stabilizer #42: Heterocyclic ring(s) containing one or two
Heterocyclic Rings containing One or Two sulfur atoms. In addition,
ligand contains Sulfur Atoms at least one additional additional
oxygen-containing rings that Oxygen Atom Binding Site in a separate
constitute O binding sites. Can include other Ring (S--O
Bidentates, S--O Tridentates, S--O ring systems bound to the
O-containing Tetradentates, or S--O Hexadentates) heterocyclic
rings, but they do not coordinate with the stabilized, high valence
metal ion. Ring(s) can also contain O, N, P, As, or Se atoms. This
5-membered ring(s) and/or additional O-containing ring(s) and/or
attached, uncoordinating rings may or may not have halogen or
polarizing or water- insolubilizing/solubilizing groups attached.
S--O Valence Stabilizer #43: Macrocyclic ligands containing two to
ten Two-, Three-, Four-, Five-, Six-, Seven-, sulfur or oxygen
binding sites to valence Eight-, Nine-, and Ten-Membered stabilize
the central metal ion. Can include Macrocyclics, Macrobicyclics,
and other hydrocarbon or ring systems bound to this
Macropolycyclics (including Catapinands, macrocyclic ligand, but
they do not coordinate Cryptands, Cyclidenes, and Sepulchrates)
with the stabilized, high valence metal ion. wherein all Binding
Sites are composed of This ligand and/or attached, uncoordinating
Sulfur (usually thiol, mercapto, or hydrocarbons/rings may or may
not have thiocarbonyl groups) or Oxygen (hydroxy, halogen or
polarizing or water- carboxy, or carbonyl groups) and are not
insolubilizing/solubilizing groups attached. contained in Component
Heterocyclic Rings (S--O Bidentates, S--O Tridentates, S--O
Tetradentates, and S--O Hexadentates) S--O Valence Stabilizer #44:
Macrocyclic ligands containing a total of four to Four-, Five-,
Six-, Seven-, Eight-, Nine-, or ten five-membered heterocyclic
rings Ten-Membered Macrocyclics, containing sulfur or oxygen
binding sites. Can Macrobicyclics, and Macropolycyclics include
other hydrocarbon/ring systems bound (including Catapinands,
Cryptands, to this macrocyclic ligand, but they do not Cyclidenes,
and Sepulchrates) wherein all coordinate with the stabilized, high
valence Binding Sites are composed of Sulfur or metal ion. This
ligand and/or attached, Oxygen and are contained in Component 5-
uncoordinating hydrocarbon/rings may or may Membered Heterocyclic
Rings (S--O not have halogen or polarizing or water- Tridentates,
S--O Tetradentates or S--O insolubilizing groups attached.
Hexadentates) S--O Valence Stabilizer #45: Macrocyclic ligands
containing at least one Four-, Five-, Six-, Seven-, Eight-, Nine-,
or heterocyclic ring. These heterocyclic rings Ten-Membered
Macrocyclics, provide sulfur or oxygen binding sites to
Macrobicyclics, and Macropolycyclics valence stabilize the central
metal ion. Other (including Catapinands, Cryptands, thiol,
mercapto, thiocarbonyl, hydroxy, Cyclidenes, and Sepulchrates)
wherein all carboxy, or carbonyl binding sites can also be Binding
Sites are composed of Sulfur or included in the macrocyclic ligand,
so long as Oxygen and are contained in a the total number of
binding sites is four to ten. Combination of Heterocyclic Rings and
Can include other hydrocarbon/ring systems Thiol, Mercapto,
Thiocarbonyl, Hydroxy, bound to this macrocyclic ligand, but they
do Carboxy, and Carbonyl Groups (S--O not coordinate with the
stabilized, high valence Tridentates, S--O Tetradentates, or S--O
metal ion. This ligand and/or attached, Hexadentates)
uncoordinating hydrocarbon/rings may or may not have halogen or
polarizing or water-
insolubilizing groups attached. S--O Valence Stabilizer #46:
Sulfoxides (R--SO--R'), where R and R' Sulfoxides (S--O Bidentates)
represent H or any organic functional group wherein the number of
carbon atoms ranges from 0 to 35, optionally having halogen or
polarizing or water-insolubilizing/solubilizing groups attached.
S--O Valence Stabilizer #47: Sulfones (R--SO.sub.2--R'), where R
and R' represent Sulfones (S--O Bidentates) H or any organic
functional group wherein the number of carbon atoms ranges from 0
to 35, optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. S--O Valence
Stabilizer #48: Sulfur dioxide ligands (--SO.sub.2) bound directly
to Sulfur dioxide (SO.sub.2) ligands (S--O the high valence metal
ion. Bidentates) N--P Valence Stabilizer #1:
[R(--NR'R'')(--PR'''R'''')], [R(--NR'R'').sub.x].sub.1-3P, [R
Aminoaryl Phosphines and Iminoaryl --NR'R'').sub.x].sub.1-3PX, or
[R(--PR'R'').sub.x].sub.1-3N, where X = Phosphines (N--P
Bidentates, N--P O or S and R, R', R'', R''', and R'''' represents
Tridentates, and N--P Tetradentates) H, NH.sub.9 or any organic
functional group wherein the number of carbon atoms ranges from 0
to 35, optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, P, O, S, or Se atoms. N--P Valence Stabilizer
#2: Five inembered heterocyclic ring(s) containing Heterocyclic
Rings containing One, Two, one, two, three, or four nitrogen atoms.
In Three, or Four Nitrogen Atoms at least one addition, ligand
contains additional additional Phosphorus Atom Binding Site
phosphorus-containing substituents that not in a Ring (N--P
Bidentates, N--P constitute P binding sites. Can include other
Tridentates, N--P Tetradentates, or N--P ring systems bound to the
heterocyclic ring or Hexadentates) to the P-containing substituent,
but they do not coordinate with the stabilized, high valence metal
ion. Ring(s) can also contain O, S, or P atoms. This ring(s) and/or
attached, uncoordinating rings and/or P-containing substituent(s)
may or may not have halogen or polarizing or
water-insolubilizing/solubilizing groups attached. N--P Valence
Stabilizer #3: Five membered heterocyclic ring(s) containing
Heterocyclic Rings containing One, Two, one, two, or three
phosphorus atoms. In or Three Phosphorus Atoms at least one
addition, ligand contains additional nitrogen- additional Nitrogen
Atom Binding Site not containing substituents (usually amines,
imines, in a Ring (N--P Bidentates, N--P Tridentates, or
hydrazides) that constitute N binding sites. N--P Tetradentates, or
N--P Hexadentates) Can include other ring systems bound to the
heterocyclic ring or to the N-containing substituent, but they do
not coordinate with the stabilized, high valence metal ion. Ring(s)
can also contain O, S, or P atoms. This ring(s) and/or attached,
uncoordinating rings and/or N- containing substituent(s) may or may
not have halogen or polarizing or water-
insolubilizing/solubilizing groups attached. N--P Valence
Stabilizer #4: Heterocyclic ring(s) containing one, two, three,
Heterocyclic Rings containing One, Two, or four nitrogen atoms. In
addition, ligand Three, or Four Nitrogen Atoms at least one
contains additional phosphorus-containing rings additional
Phosphorus Atom Binding Site that constitute P binding sites. Can
include in a Separate Ring (N--P Bidentates, N--P other ring
systems bound to the N- or P- Tridentates, N--P Tetradentates)
containing heterocyclic rings, but they do not coordinate with the
stabilized, high valence metal ion. Ring(s) can also contain O, S,
or P atoms. This ring(s) and/or additional P- containing ring(s)
and/or attached, uncoordinating rings may or may not have halogen
or polarizing or water- insolubilizing/solubilizing groups
attached. N--P Valence Stabilizer #5: Macrocyclic ligands
containing two, three, four, Two-, Three-, Four-, Five-, Six-,
Seven-, five, six, seven, eight, nine, or ten binding sites Eight-,
Nine-, and Ten-Membered composed of nitrogen and phosphorus to
Macrocyclics, Macrobicyclics, and valence stabilize the central
metal ion. Can Macropolycyclics (including Catapinands, include
other hydrocarbon or ring systems Cryptands, Cyclidenes, and
Sepulchrates) bound to this macrocyclic ligand, but they do wherein
all Binding Sites are composed of not coordinate with the
stabilized, high valence Nitrogen (usually amine or imine groups)
metal ion. This ligand and/or attached, or Phosphorus and are not
contained in uncoordinating hydrocarbons/rings may or may Component
Heterocyclic Rings (N--P not have halogen or polarizing or water-
Bidentates, N--P Tridentates, N--P insolubilizing/solubilizing
groups attached. Tetradentates, and N--P Hexadentates) N--P Valence
Stabilizer #6: Macrocyclic ligands containing a total of four,
Four-, Five-, Six-, Seven-, Eight-, Nine-, five, six, seven, eight,
nine, or ten heterocyclic or Ten-Membered Macrocyclics, rings
containing nitrogen or phosphorus binding Macrobicyclics, and
Macropolycyclics sites. Can include other hydrocarbon/ring
(including Catapinands, Cryptands, systems bound to this
macrocyclic ligand, but Cyclidenes, and Sepulchrates) wherein all
they do not coordinate with the stabilized, high Binding Sites are
composed of Nitrogen or valence metal ion. This ligand and/or
attached, Phosphorus and are contained in uncoordinating
hydrocarbon/rings may or may Component Heterocyclic Rings (N--P not
have halogen or polarizing or water- Bidentates, N--P Tridentates,
N--P insolubilizing groups attached. Tetradentates, or N--P
Hexadentates) N--P Valence Stabilizer #7: Macrocyclic ligands
containing at least one Four-, Five-, Six-, Seven-, Eight-, Nine-,
or heterocyclic ring. These heterocyclic rings Ten-Membered
Macrocyclics, provide nitrogen or phosphorus binding sites to
Macrobicyclics, and Macropolycyclics valence stabilize the central
metal ion. Other (including Catapinands, Cryptands, amine, imine,
or phosphine binding sites can Cyclidenes, and Sepulchrates)
wherein all also be included in the macrocyclic ligand, so Binding
Sites are composed of Nitrogen or long as the total number of
binding sites is four, Phosphorus and are contained in a five, six,
seven, eight, nine, or ten. Can include Combination of Heterocyclic
Rings and other hydrocarbon/ring systems bound to this Amine,
Imine, and Phosphine Groups (N--P macrocyclic ligand, but they do
not coordinate Bidentates, N--P Tridentates, N--P with the
stabilized, high valence metal ion. Tetradentates, or N--P
Hexadentates) This ligand and/or attached, uncoordinating
hydrocarbon/rings may or may not have halogen or polarizing or
water-insolubilizing groups attached. S--P Valence Stabilizer #1:
[R(--SR').sub.x].sub.1-3P, [R(--SR').sub.x].sub.1-3PX, [R(--PR'R'')
Thioaryl Phosphines (S--P Bidentates, S--P (--SR''')],
[R(--PR'R'')(--S--S--R''')], [R(--PR--R'') Tridentates, and S--P
Tetradentates) (--C(.dbd.S)R'''],
[R(--PR'R'').sub.x].sub.x].sub.2S, [R(--PR'R'').sub.x].sub.2-3
R'''(--SR'''').sub.y,
]R--SR').sub.x.sub.2-3R''(--PR'''R'''').sub.y,[R
(--PR'R'').sub.x].sub.2S.sub.2, and
[R(--PR'R'').sub.x].sub.2R'''(C(.dbd.S)).sub.yR'''', where X = O or
S, and R, R', R'', R''', and R'''' represent H, NH.sub.2, or any
organic functional group wherein the number of carbon atoms ranges
from 0 to 40, optionally having halogen or polarizing or water-
insolubilizing/solubilizing groups attached, and x = 1-2 and y =
1-4. Ligand can also contain nonbinding N, O, S, or P atoms. S--P
Valence Stabilizer #2: Heterocyclic ring(s) containing one or two
Heterocyclic Rings containing One or Two sulfur atoms. In addition,
ligand contains Sulfur Atoms at least one additional additional
phosphorus-containing substituents Phosphorus Atom Binding Site not
in a that constitute P binding sites. Can include Ring (P--S
Bidentates, P--S Tridentates, P--S other ring systems bound to the
heterocyclic Tetradentates, or P-S Hexadentates) ring or to the
P-containing substituent, but they do not coordinate with the
stabilized, high valence metal ion. Ring(s) can also contain O, S,
or P atoms. This ring(s) and/or attached, uncoordinating rings
and/or P-containing substituent(s) may or may not have halogen or
polarizing or water-insolubilizing/solubilizing groups attached.
S--P Valence Stabilizer #3: Heterocyclic ring(s) containing one,
two, or Heterocyclic Rings containing One, Two, three phosphorus
atoms. In addition, ligand or Three Phosphorus Atoms at least one
contains additional sulfur-containing additional Sulfur Atom
Binding Site not in substituents (usually thiol, mercapto, or a
Ring (S--P Bidentates, S--P Tridentates, thiocarbonyl groups) that
constitute S binding S--P Tetradentates, or S--P Hexadentates)
sites. Can include other ring systems bound to the heterocyclic
ring or to the S-containing substituent, but they do not coordinate
with the stabilized, high valence metal ion. Ring(s) can also
contain O, S, or P atoms. This ring(s) and/or attached,
uncoordinating rings and/or S- containing substituent(s) may or may
not have halogen or polarizing or water-
insolubilizing/solubilizing groups attached. S--P Valence
Stabilizer #4: Heterocyclic ring(s) containing one or two
Heterocyclic Rings containing One or Two sulfur atoms. In addition,
ligand contains Sulfur Atoms at least one additional additional
phosphorus-containing rings that Phosphorus Atom Binding Site in a
constitute P binding sites. Can include other Separate Ring (S--P
Bidentates, S--P ring systems bound to the S- or P-containing
Tridentates, S--P Tetradentates) heterocyclic rings, but they do
not coordinate with the stabilized, high valence metal ion. Ring(s)
can also contain O, S, or P atoms. This ring(s) and/or additional
P-containing ring(s) and/or attached, uncoordinating rings may or
may not have halogen or polarizing or water-
insolubilizing/solubilizing groups attached. S--P Valence
Stabilizer #5: Macrocyclic ligands containing two, three, four,
Two-, Three-, Four-, Five-, Six-, Seven-, five, six, seven, eight,
nine, or ten binding sites Eight-, Nine-, and Ten-Membered composed
of sulfur and phosphorus to valence Macrocyclics, Macrobicyclics,
and stabilize the central metal ion. Can include Macropolycyclics
(including Catapinands, other hydrocarbon or ring systems bound to
this Cryptands, Cyclidenes, and Sepulchrates) macrocyclic ligand,
but they do not coordinate wherein all Binding Sites are composed
of with the stabilized, high valence metal ion. Sulfur (usually
thiol, mercapto, or This ligand and/or attached, uncoordinating
thiocarbonyl groups) or Phosphorus and are hydrocarbons/rings may
or may not have not contained in Component Heterocyclic halogen or
polarizing or water- Rings (S--P Bidentates, S--P Tridentates, S--P
insolubilizing/solubilizing groups attached. Tetradentates, and
S--P Hexadentates) S--P Valence Stabilizer #6: Macrocyclic ligands
containing a total of
four, Four-, Five-, Six-, Seven-, Eight-, Nine-, or five, six,
seven, eight, nine, or ten heterocyclie Ten-Membered Macrocyclics,
rings containing sulfur or phosphorus binding Macrobicyclics, and
Macropolycyclics sites. Can include other hydrocarbon/ring
(including Catapinands, Cryptands, systems bound to this
macrocyclic ligand, but Cyclidenes, and Sepulchrates) wherein all
they do not coordinate with the stabilized, high Binding Sites are
composed of Sulfur or valence metal ion. This ligand and/or
attached, Phosphorus and are contained in uncoordinating
hydrocarbon/rings may or may Component Heterocyclic Rings (S--P not
have halogen or polarizing or water- Bidentates, S--P Tridentates,
S--P insolubilizing groups attached. Tetradentates, or S--P
Hexadentates) S--P Valence Stabilizer #7: Macrocyclic ligands
containing at least one Four-, Five-, Six-, Seven-, Eight-, Nine-,
or heterocyclic ring. These heterocyclic rings Ten-Membered
Macrocyclics, provide sulfur or phosphorus binding sites to
Macrobicyclics, and Macropolycyclics valence stabilize the central
metal ion. Other (including Catapinands, Cryptands, thiol,
mercapto, or thiocarbonyl, or phosphine Cyclidenes, and
Sepulchrates) wherein all binding sites can also be included in the
Binding Sites are composed of Sulfur or macrocyclic ligand, so long
as the total number Phosphorus and are contained in a of binding
sites is four, five, six, seven, eight, Combination of Heterocyclic
Rings and nine, or ten. Can include other Thiol, Mercapto,
Thiocarbonyl or hydrocarbon/ring systems bound to this Phosphine
Groups (S--P Bidentates, S--P macrocyclic ligand, but they do not
coordinate Tridentates, S--P Tetradentates, or S--P with the
stabilized, high valence metal ion. Hexadentates) This ligand
and/or attached, uncoordinating hydrocarbon/rings may or may not
have halogen or polarizing or water-insolubilizing groups attached.
P--O Valence Stabilizer #1: [R(--OR').sub.x],.sub.1-3P,
[R(--OR').sub.x].sub.1-3PX, [R(--PR'R'') Hydroxyaryl Phosphines
(P--O Bidentates, (--OR''')], [R(--PR'R'')(--C(.dbd.O)R'''], [R
P--O Tridentates, and P--O Tetradentates)
(--RPR'R'').sub.x].sub.2O,
[R(--PR'R'').sub.x].sub.2-3R'''(--OR'''').sub.y, [R
(--OR').sub.x].sub.2-3R''(--PR'''R'''').sub.y, and [R
(--PR'R'').sub.x].sub.2R'''(C(.dbd.O)),R'''', where X = O or S, and
R, R', R'', R''', and R'''' represent H, NH.sub.2, or any organic
functional group wherein the number of carbon atoms ranges from 0
to 40, optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached, and x = 1-2 and
y = 1-4. Ligand can also contain nonbinding N, O, S, or P atoms.
P--O Valence Stabilizer #2: Heterocyclic ring(s) containing one or
two Heterocyclic Rings containing One or Two oxygen atoms. In
addition, ligand contains Oxygen Atoms at least one additional
additional phosphorus-containing substituents Phosphorus Atom
Binding Site not in a that constitute P binding sites. Can include
Ring (P--O Bidentates, P--O Tridentates, P--O other ring systems
bound to the heterocyclic Tetradentates, or P--O Hexadentates) ring
or to the P-containing substituent, but they do not coordinate with
the stabilized, high valence metal ion. Ring(s) can also contain O,
S, or P atoms. This ring(s) and/or attached, uncoordinating rings
and/or P-containing substituent(s) may or may not have halogen or
polarizing or water-insolubilizing/solubilizing groups attached.
P--O Valence Stabilizer #3: Heterocyclic ring(s) containing one,
two, or Heterocyclic Rings containing One, Two, three phosphorus
atoms. In addition, ligand or Three Phosphorus Atoms at least one
contains additional oxygen-containing additional Oxygen Atom
Binding Site not substituents (usually hydroxy, carboxy, or in a
Ring (P--O Bidentates, P--O Tridentates, carbonyl groups) that
constitute 0 binding sites. P--O Tetradentates, or P--O
Hexadentates) Can include other ring systems bound to the
heterocyclic ring or to the O-containing substituent, hut they do
not coordinate with the stabilized, high valence metal ion. Ring(s)
can also contain O, S, or P atoms. This ring(s) and/or attached,
uncoordinating rings and/or O- containing substituent(s) may or may
not have halogen or polarizing or water-
insolubilizing/solubilizing groups attached. P--O Valence
Stabilizer #4: Heterocyclic ring(s) containing one or two
Heterocyclic Rings containing One or Two oxygen atoms. In addition,
ligand contains Oxygen Atoms at least one additional additional
phosphorus-containing rings that Phosphorus Atom Binding Site in a
constitute P binding sites. Can include other Separate Ring (P--O
Bidentates, P--O ring systems bound to the O- or P-containing
Tridentates, P--O Tetradentates) heterocyclic rings, but they do
not coordinate with the stabilized, high valence metal ion. Ring(s)
can also contain O, S, or P atoms. This ring(s) and/or additional
P-containing ring(s) and/or attached, uncoordinating rings may or
may not have halogen or polarizing or water-
insolubilizing/solubilizing groups attached. P--O Valence
Stabilizer #5: Macrocyclic ligands containing two, three, four,
Two-, Three-, Four-, Five-, Six-, Seven-, five, six, seven, eight,
nine, or ten binding sites Eight-, Nine-, and Ten-Membered composed
of oxygen and phosphorus to valence Macrocyclics, Macrobicyclics,
and stabilize the central metal ion. Can include Macropolycyclics
(including Catapinands, other hydrocarbon or ring systems bound to
this Cryptands, Cyclidenes, and Sepulchrates) macrocyclic ligand,
but they do not coordinate wherein all Binding Sites are composed
of with the stabilized, high valence metal ion. Oxygen (usually
hydroxy, carboxy, or This ligand and/or attached, uncoordinating
carbonyl groups) or Phosphorus and are not hydrocarbons/rings may
or may not have contained in Component Heterocyclic halogen or
polarizing or water- Rings (P--O Bidentates, P--O Tridentates,
insolubilizing/solubilizing groups attached. 0 Tetradentates, and
P--O Hexadentates) P--O Valence Stabilizer #6: Macrocyclic ligands
containing a total of four, Four-, Five-, Six-, Seven-, Eight-,
Nine-, or five, six, seven, eight, nine, or ten heterocyclic
Ten-Membered Macrocyclics, rings containing oxygen or phosphorus
binding Macrobicyclics, and Macropolycyclics sites. Can include
other hydrocarbon/ring (including Catapinands, Cryptands, systems
bound to this macrocyclic ligand, but Cyclidenes, and Sepulchrates)
wherein all they do not coordinate with the stabilized, high
Binding Sites are composed of Oxygen or valence metal ion. This
ligand and/or attached, Phosphorus and are contained in
uncoordinating hydrocarbon/rings may or may Component Heterocyclic
Rings (P--O not have halogen or polarizing or water- Bidentates,
P--O Tridentates, P--O insolubilizing groups attached. P--O
Tetradentates, or P--O Hexadentates) P--O Valence Stabilizer #7:
Macrocyclic ligands containing at least one Four-, Five-, Six-,
Seven-, Eight-, Nine-, or heterocyclic ring. These heterocyclic
rings Ten-Membered Macrocyclics, provide oxygen or phosphorus
binding sites to Macrobicyclics, and Macropolycyclics valence
stabilize the central metal ion. Other (including Catapinands,
Cryptands, hydroxy, carboxy, carbonyl, or phosphine Cyclidenes, and
Sepulchrates) wherein all binding sites can also be included in the
Binding Sites are composed of Oxygen or macrocyclic ligand, so long
as the total number Phosphorus and are contained in a of binding
sites is four, five, six, seven, eight, Combination of Heterocyclic
Rings and nine, or ten. Can include other Hydroxy, Carboxy,
Carbonyl or Phosphine hydrocarbon/ring systems bound to this Groups
(P--O Bidentates, P--O Tridentates, macrocyclic ligand, but they do
not coordinate P--O Tetradentates, or P--O Hexadentates) with the
stabilized, high valence metal ion. This ligand and/or attached,
uncoordinating hydrocarbon/rings may or may not have halogen or
polarizing or water-insolubilizing groups attached. As Valence
Stabilizer #1: AsH.sub.3, AsH.sub.2R, AsHR.sub.2, where R
represents H or Monoarsines (As Monodentates) wherein at any
organic functional group wherein the least one Arsenic Atom is a
Binding Site number of carbon atoms ranges from 0 to 25, optionally
having halogen or polarizing or water-insolubilizing/solubilizing
groups attached. Ligand can also contain nonbinding N, P, As, O, S,
or Se atoms. As Valence Stabilizer #2: R'--As--R--As--R'', where R,
R', and R'' represent Diarsines (an As--As Bidentate) wherein at H
or any organic functional group wherein the least one Arsenic Atom
is a Binding Site number of carbon atoms ranges from 0 to 25,
optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, P, As, O, S, or Se atoms. As Valence
Stabilizer #3: R--As--R'--As--R''--As--R''', where R, R', R'', and
Triarsines (either As--As Bidentates or R''' represent H or any
organic functional group As--As Tridentates) wherein at least one
wherein the number of carbon atoms ranges Arsenic Atom is a Binding
Site from 0 to 25, optionally having halogen or polarizing or
water-insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, P, As, O, S, or Se atoms. As Valence
Stabilizer #4: R--As--R'--As--R''--As--R'''--As--R'''', where R,
R', Tetraarsines (As--As Bidentates, As--As R'', R''', and R''''
represent H or any organic Tridentates, or As--As Tetradentates)
functional group wherein the number of carbon wherein at least one
Arsenic Atom is a atoms ranges from 0 to 25, optionally having
Binding Site halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, P, As, O, S, or Se atoms. As Valence
Stabilizer #5: R--As--R'--As--R''--As--R''' Pentaarsines (As--As
Bidentates, As--As where R, R', R'', R''', R'''', and R'''''
represent Tridentates, or As--As Tetradentates) H or any organic
functional group wherein the wherein at least one Arsenic Atom is a
number of carbon atoms ranges from 0 to 25, Binding Site optionally
having halogen or polarizing or water-insolubilizing/solubilizing
groups attached. Ligand can also contain nonbinding N, P, As, O, S,
or Se atoms. As Valence Stabilizer #6:
R--As--R'--As--R''--As--R'''--As--R''''--As--R'''''--As--
Hexaarsines (As--As Bidentates, As--As R'''''', where R, R', R'',
R''', R'''', R''''', and Tridentates, As--As Tetradentates, or
As--As R'''''' represent H or any organic functional Hexadentates)
wherein at least one Arsenic group wherein the number of carbon
atoms Atom is a Binding Site ranges from 0 to 25, optionally having
halogen or polarizing or water- insolubilizing/solubilizing groups
attached. Ligand can also contain nonbinding N, P, As, O, S, or Se
atoms. As Valence Stabilizer #7: Five membered heterocyclic ring
containing Five-Membered Heterocyclic Rings just one arsenic
binding site. Can include other containing One Arsenic Atom wherein
the ring systems bound to this heterocyclic ring, but Arsenic Atom
is the Binding Site (As they do not coordinate with the stabilized,
high Monodentates) valence metal ion. Ring can also contain O,
S,
N, P, or Se atoms. This 5-membered ring and/or attached,
uncoordinating rings may or may not have halogen or polarizing or
water- insolubilizing/solubilizing groups attached. As Valence
Stabilizer #8: Six membered heterocyclic nng containing just
Six-Membered Heterocyclic Rings one arsenic binding site. Can
include other ring containing One Arsenic Atom wherein the systems
bound to this heterocyclic ring, but they Arsenic Atom is the
Binding Site (As do not coordinate with the stabilized, high
Monodentates) valence metal ion. Ring can also contain O, S, N, P,
or Se atoms. This 6-membered ring and/or attached, uncoordinating
rings may or may not have halogen or polarizing or water-
insolubilizing/solubilizing groups attached. As Valence Stabilizer
#9: Five membered heterocyclic ring(s) containing Five-Membered
Heterocyclic Rings one arsenic atom. In addition, ligand contains
containing One Arsenic Atom and having additional
arsenic-containing substituents at least one additional Arsenic
Atom (usually arsines) that constitute As binding Binding Site not
in a Ring (As sites. Can include other ring systems bound to
Monodentates, As--As Bidentates, As--As the heterocyclic ring or to
the As-containing Tridentates, As--As Tetradentates, or As--As
substituent, but they do not coordinate with the Hexadentates)
stabilized, high valence metal ion. Ring(s) can also contain O, N,
S, P or Se atoms. This 5- membered ring(s) and/or attached,
uncoordinating rings and/or As-containing substituent(s) may or may
not have halogen or polarizing or water-insolubilizing/solubilizing
groups attached. As Valence Stabilizer #10: Six membered
heterocyclic ring(s) containing Six-Membered Heterocyclic Rings one
arsenic atom. In addition, ligand contains containing One Arsenic
Atom and having additional arsenic-containing substituents at least
one additional Arsenic Atom (usually arsines) that constitute As
binding Binding Site not in a Ring (As sites. Can include other
ring systems bound to Monodentates, As--As Bidentates, As--As the
heterocyclic ring or to the As-containing Tridentates, As--As
Tetradentates, or As--As substituent, but they do not coordinate
with the Hexadentates) stabilized, high valence metal ion. Ring(s)
can also contain O, N, S, P or Se atoms. This 6- membered ring(s)
and/or attached, uncoordinating rings and/or As-containing
substituent(s) may or may not have halogen or polarizing or
water-insolubilizing/solubilizing groups attached. As Valence
Stabilizer #11: Five membered heterocyclic ring(s) containing
Five-Membered Heterocyclic Rings one arsenic atom. In addition,
ligand contains containing One Arsenic Atom and having additional
arsenic-containing rings that at least one additional Arsenic Atom
constitute As binding sites. Can include other Binding Site in a
separate Ring (As ring systems bound to the As-containing
Monodentates, As--As Bidentates, As--As heterocyclic rings, but
they do not coordinate Tridentates, As--As Tetradentates, or As--As
with the stabilized, high valence metal ion. Hexadentates) Ring(s)
can also contain O, N, S, P, or Se atoms. This 5-membered ring(s)
and/or additional As-containing ring(s) and/or attached,
uncoordinating rings may or may not have halogen or polarizing or
water- insolubilizing/solubilizing groups attached. As Valence
Stabilizer #12: Six membered heterocyclic ring(s) containing
Six-Membered Heterocyclic Rings one arsenic atom. In addition,
ligand contains containing One Arsenic Atom and having additional
arsenic-containing rings that at least one additional Arsenic Atom
constitute As binding sites. Can include other Binding Site in a
separate Ring (As ring systems bound to the As-containing
Monodentates, As--As Bidentates, As--As heterocyclic rings, but
they do not coordinate Tridentates, As--As Tetradentates, or As--As
with the stabilized, high valence metal ion. Hexadentates) Ring(s)
can also contain O, N, S, P, or Se atoms. This 6-membered ring(s)
and/or additional As-containing ring(s) and/or attached,
uncoordinating rings may or may not have halogen or polarizing or
water- insolubilizing/solubilizing groups attached. As Valence
Stabilizer #13: Macrocyclic ligands containing two, three, four,
Two-, Three-, Four-, and Six-Membered or six arsenic binding sites
to valence stabilize Macrocyclics, Macrobicyclics, and the central
metal ion. Can include other Macropolycyclics (including
Catapinands, hydrocarbon or ring systems bound to this Cryptands,
Cyclidenes, and Sepulchrates) macrocyclic ligand, but they do not
coordinate wherein all Binding Sites are composed of with the
stabilized, high valence metal ion. Arsenic and are not contained
in This ligand and/or attached, uncoordinating Component
Heterocyclic Rings (As--As hydrocarbons/rings may or may not have
Bidentates, As--As Tridentates, As--As halogen or polarizing or
water- Tetradentates, and As--As Hexadentates)
insolubilizing/solubilizing groups attached. As Valence Stabilizer
#14: Macrocyclic ligands containing a total of four Four-, or
Six-Membered Macrocyclics, or six five-membered heterocyclic rings
Macrobicyclics, and Macropolycyclics containing arsenic binding
sites. Can include (including Catapinands, Cryptands, other
hydrocarbon/ring systems bound to this Cyclidenes, and
Sepulchrates) wherein all macrocyclic ligand, but they do not
coordinate Binding Sites are composed of Arsenic and with the
stabilized, high valence metal ion. are contained in Component
5-Membered This ligand and/or attached, uncoordinating Heterocyclic
Rings (As--As Tridentates, hydrocarbon/rings may or may not have
As--As Tetradentates, or As--As Hexadentates) halogen or polarizing
or water-insolubilizing groups attached. As Valence Stabilizer #15:
Macrocyclic ligands containing at least one 5- Four-, or
Six-Membered Macrocyclics, membered heterocyclic ring. These
Macrobicyclics, and Macropolycyclics heterocyclic rings provide
arsenic binding sites (including Catapinands, Cryptands, to valence
stabilize the central metal ion. Other Cyclidenes, and
Sepulchrates) wherein all arsine binding sites can also be included
in the Binding Sites are composed of Arsenic and macrocyclic
ligand, so long as the total number are contained in a Combination
of 5- of binding sites is four or eight. Can include Membered
Heterocyclic Rings and Arsine other hydrocarbon/ring systems bound
to this Groups (As--As Tridentates, As--As macrocyclic ligand, but
they do not coordinate Tetradentates, or As--As Hexadentates) with
the stabilized, high valence metal ion. This ligand and/or
attached, uncoordinating hydrocarbon/rings may or may not have
halogen or polarizing or water-insolubilizing groups attached. As
Valence Stabilizer #16: Macrocyclic ligands containing a total of
four Four-, or Six-Membered Macrocyclics, or six six-membered
heterocyclic rings Macrobicyclics, and Macropolycyclics containing
arsenic binding sites. Can include (including Catapinands,
Cryptands, other hydrocarbon/ring systems bound to this Cyclidenes,
and Sepulchrates) wherein all macrocyclic ligand, but they do not
coordinate Binding Sites are composed of Arsenic and with the
stabilized, high valence metal ion. are contained in Component
6-Membered This ligand and/or attached, uncoordinating Heterocyclic
Rings (As--As Tridentates, hydrocarbon/rings may or may not have
As--As Tetradentates, or As--As Hexadentates) halogen or polarizing
or water-insolubilizing groups attached. As Valence Stabilizer #17:
Macrocyclic ligands containing at least one 6- Four-, or
Six-Membered Macrocyclics, membered heterocyclic ring. These
Macrobicyclics, and Macropolycyclics heterocyclic rings provide
arsenic binding sites (including Catapinands, Cryptands, to valence
stabilize the central metal ion. Other Cyclidenes, and
Sepulchrates) wherein all arsine binding sites can also be included
in the Binding Sites are composed of Arsenic and macrocyclic
ligand, so long as the total number are contained in a Combination
of 6- of binding sites is four or six. Can include Membered
Heterocyclic Rings and Arsine other hydrocarbon/ring systems bound
to this Groups (As--As Tridentates, As--As macrocyclic ligand, but
they do not coordinate Tetradentates, or As--As Hexadentates) with
the stabilized, high valence metal ion. This ligand and/or
attached, uncoordinating hydrocarbon/rings may or may not have
halogen or polarizing or water-insolubilizing groups attached. Se
Valence Stabilizer #1: SeH.sub.2, SeHR, SeR.sub.2, where R
represents H or any Monoselenoethers (Se Monodentates) organic
functional group wherein the number of wherein at least one
Selenium Atom is a carbon atoms ranges from 0 to 25, optionally
Binding Site having halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, P, O, S, or Se atoms. Se Valence Stabilizer
#2: R--Se--R'--Se--R'', where R, R', and R'' represents
Diselenoethers (Se--Se Bidentates) wherein H or any organic
functional group wherein the at least one Selenium Atom is a
Binding number of carbon atoms ranges from 0 to 25, Site optionally
having halogen or polarizing or water-insolubilizing/solubilizing
groups attached. Ligand can also contain nonbinding N, P, O, S, or
Se atoms. Se Valence Stabilizer #3: R--Se--R'--Se--R''--Se--R''',
where R, R', R'', and Triselenoethers (Se--Se Bidentates or Se--Se
R''' represents H or any organic functional Tridentates) wherein at
least one Selenium group wherein the number of carbon atoms Atom is
a Binding Site ranges from 0 to 25, optionally having halogen or
polarizing or water- insolubilizing/solubilizing groups attached.
Ligand can also contain nonbinding N, P, O, S, or Se atoms. Se
Valence Stabilizer #4: R--Se--R'--Se--R''--Se--R'''--Se--R'''',
where R, R', Tetraselenoethers (Se--Se Bidentates, Se--Se R'',
R''', and R'''' represents H or any organic Tridentates, or Se--Se
Tetradentates) functional group wherein the number of carbon
wherein at least one Selenium Atom is a atoms ranges from 0 to 25,
optionally having Binding Site halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, P, O, S, or Se atoms. Se Valence Stabilizer
#5: Five membered heterocyclic ring containing Five-Membered
Heterocyclic Rings one or two selenium atoms, both of which may
containing One or Two Selenium Atoms function as binding sites. Can
include other wherein at least one Selenium Atom is a ring systems
bound to this heterocyclic ring, but Binding Site (Se Monodentates
or Se--Se they do not coordinate with the stabilized, high
Bidentates) valence metal ion. Ring can also contain O, N, P, As,
or S atoms. This 5-membered ring and/or attached, uncoordinating
rings may or may not have halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Se Valence Stabilizer
#6: Six membered heterocyclic ring containing one
Six-Membered Heterocyclic Rings or two selenium atoms, both of
which may containing One or Two Selenium Atoms function as binding
sites. Can include other wherein at least one Selenium Atom is a
ring systems bound to this heterocyclic ring, but Binding Site (Se
Monodentates or Se--Se they do not coordinate with the stabilized,
high Bidentates) valence metal ion. Ring can also contain O, N, P,
As, or S atoms. This 5-membered ring and/or attached,
uncoordinating rings may or may not have halogen or polarizing or
water- insolubilizing/solubilizing groups attached. Se Valence
Stabilizer #7: Five membered heterocyclic ring(s) containing
Five-Membered Heterocyclic Rings one selenium atom. In addition,
ligand contains containing One Selenium Atom and having additional
selenium-containing substituents at least one additional Selenium
Atom (usually selenols or selenoethers) that constitute Binding
Site not in a Ring (Se Se binding sites. Can include other ring
Monodentates, Se--Se Bidentates, Se--Se systems bound to the
heterocyclic ring or to the Tridentates, Se--Se Tetradentates, or
Se--Se Se-containing substituent, but they do not Hexadentates)
coordinate with the stabilized, high valence metal ion. Ring(s) can
also contain O, N, P, As or S atoms. This 5-membered ring(s) and/or
attached, uncoordinating rings and/or Se- containing substituent(s)
may or may not have halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Se Valence Stabilizer
#8: Six membered heterocyclic ring(s) containing Six-Membered
Heterocyclic Rings one selenium atom. In addition, ligand contains
containing One Selenium Atom and having additional
selenium-containing substituents at least one additional Selenium
Atom (usually selenols or selenoethers) that constitute Binding
Site not in a Ring (Se Se binding sites. Can include other ring
Monodentates, Se--Se Bidentates, Se--Se systems bound to the
heterocyclic ring or to the Tridentates, Se--Se Tetradentates, or
Se--Se Se-containing substituent, but they do not Hexadentates)
coordinate with the stabilized, high valence metal ion. Ring(s) can
also contain O, N, P, As or S atoms. This 6-membered ring(s) and/or
attached, uncoordinating rings and/or Se- containing substituent(s)
may or may not have halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Se Valence Stabilizer
#9: Five membered heterocyclic ring(s) containing Five-Membered
Heterocyclic Rings one selenium atom. In addition, ligand contains
containing One Selenium Atom and having additional
selenium-containing rings that at least one additional Selenium
Atom constitute Se binding sites. Can include other Binding Site in
a separate Ring (Se ring systems bound to the Se-containing
Monodentates, Se--Se Bidentates, Se--Se heterocyclic rings, but
they do not coordinate Tridentates, Se--Se Tetradentates, or Se--Se
with the stabilized, high valence metal ion. Hexadentates) Ring(s)
can also contain O, N, P, As, or S atoms. This 5-membered ring(s)
and/or additional Se-containing ring(s) and/or attached,
uncoordinating rings may or may not have halogen or polarizing or
water- insolubilizing/solubilizing groups attached. Se Valence
Stabilizer #10: Six membered heterocyclic ring(s) containing
Six-Membered Heterocyclic Rings one selenium atom. In addition,
ligand contains containing One Selenium Atom and having additional
selenium-containing rings that at least one additional Selenium
Atom constitute Se binding sites. Can include other Binding Site in
a separate Ring (Se ring systems bound to the Se-containing
Monodentates, Se--Se Bidentates, Se--Se heterocyclic rings, but
they do not coordinate Tridentates, Se--Se Tetradentates, or Se--Se
with the stabilized, high valence metal ion. Hexadentates) Ring(s)
can also contain O, N, P, As, or S atoms. This 6-membered ring(s)
and/or additional Se-containing ring(s) and/or attached,
uncoordinating rings may or may not have halogen or polarizing or
water- insolubilizing/solubilizing groups attached. Se Valence
Stabilizer #11: Macrocyclic ligands containing two, three, four,
Two-, Three-, Four-, or Six-Membered or six selenium binding sites
to valence Macrocyclics, Macrobicyclics, and stabilize the central
metal ion. Can include Macropolycyclics (including Catapinands,
other hydrocarbon or ring systems bound to this Cryptands,
Cyclidenes, and Sepulchrates) macrocyclic ligand, but they do not
coordinate wherein all Binding Sites are composed of with the
stabilized, high valence metal ion. Selenium (usually selenol or
selenoether This ligand and/or attached, uncoordinating groups) and
are not contained in hydrocarbons/rings may or may not have
Component Heterocyclic Rings (Se--Se halogen or polarizing or
water- Bidentates, Se--Se Tridentates, Se--Se
insolubilizing/solubilizing groups attached. Tetradentates, or
Se--Se Hexadentates) Se Valence Stabilizer #12: Macrocyclic ligands
containing a total of four Four-, or Six-Membered Macrocyclics, or
six five-membered heterocyclic rings Macrobicyclics, and
Macropolycyclics containing selenium binding sites. Can include
(including Catapinands, Cryptands, other hydrocarbon/ring systems
bound to this Cyclidenes, and Sepulchrates) wherein all macrocyclic
ligand, but they do not coordinate Binding Sites are composed of
Selenium with the stabilized, high valence metal ion. and are
contained in Component 5- This ligand and/or attached,
uncoordinating Membered Heterocyclic Rings (Se--Se
hydrocarbon/rings may or may not have Tridentates, Se--Se
Tetradentates or Se--Se halogen or polarizing or
water-insolubilizing Hexadentates) groups attached. Se Valence
Stabilizer #13: Macrocyclic ligands containing at least one 5-
Four-, or Six-Membered Macrocyclics, membered heterocyclic ring.
These Macrobicyclics, and Macropolycyclics heterocyclic rings
provide selenium binding (including Catapinands, Cryptands, sites
to valence stabilize the central metal ion. Cyclidenes, and
Sepulchrates) wherein all Other selenol or selenoether binding
sites can Binding Sites are composed of Selenium also be included
in the macrocyclic ligand, so and are contained in a Combination of
5- long as the total number of binding sites is four Membered
Heterocyclic Rings and Selenol or six. Can include other
hydrocarbon/ring or Selenoether Groups (Se--Se Tridentates, systems
bound to this macrocyclic ligand, but Se--Se Tetradentates, or
Se--Se they do not coordinate with the stabilized, high
Hexadentates) valence metal ion. This ligand and/or attached,
uncoordinating hydrocarbon/rings may or may not have halogen or
polarizing or water insolubilizing groups attached. Se Valence
Stabilizer #14: Macrocyclic ligands containing a total of four
Four-, or Six-Membered Macrocyclics, or six six-membered
heterocyclic rings Macrobicyclics, and Macropolycyclics containing
selenium binding sites. Can include (including Catapinands,
Cryptands, other hydrocarbon/ring systems bound to this Cyclidenes,
and Sepulchrates) wherein all macrocyclic ligand, but they do not
coordinate Binding Sites are composed of Selenium with the
stabilized, high valence metal ion. and are contained in Component
6- This ligand and/or attached, uncoordinating Membered
Heterocyclic Rings (Se--Se hydrocarbon/rings may or may not have
Tridentates, Se--Se Tetradentates, or Se--Se halogen or polarizing
or water-insolubilizing Hexadentates) groups attached. Se Valence
Stabilizer #15: Macrocyclic ligands containing at least one 6-
Four-, or Six-Membered Macrocyclics, membered heterocyclic ring.
These Macrobicyclics, and Macropolycyclics heterocyclic rings
provide selenium binding (including Catapinands, Cryptands, sites
to valence stabilize the central metal ion. Cyclidenes, and
Sepulchrates) wherein all Other selenol or selenoether binding
sites can Binding Sites are composed of Selenium also be included
in the macrocyclic ligand, so and are contained in a Combination of
6- long as the total number of binding sites is four Membered
Heterocyclic Rings and Selenol or six. Can include other
hydrocarbon/ring or Selenoether Groups (Se--Se Tridentates, systems
bound to this macrocyclic ligand, but Se--Se Tetradentates, or
Se--Se they do not coordinate with the stabilized, high
Hexadentates) valence metal ion. This ligand and/or attached,
uncoordinating hydrocarbon/rings may or may not have halogen or
polarizing or water- insolubilizing groups attached. Se Valence
Stabilizer #16: R--C(.dbd.Se)--CR'R''--C(.dbd.Se)--R''' where R,
R', R'', 1,3-Diselenoketones (Diseleno-beta- and R''' represent H,
NH.sub.2, or any organic ketonates), 1,3,5-Triselenoketones,
Bis(1,3- functional group wherein the number of carbon
Diselenoketones), and Poly(1,3- atoms ranges from 0 to 40,
optionally having Diselenoketones) (S--S Bidentates, S--S halogen
or polarizing or water- Tridentates, S--S Tetradentates)
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. Se Valence Stabilizer #17:
RR'--C.dbd.C(--Se)(--Se), where R and R' represent
1,1-Diselenolates, Bis(1,1-diselenolates), H, NH.sub.2 or any
organic functional group wherein and Poly(1,1-diselenolates)
(Se--Se the number of carbon atoms ranges from 0 to Bidentates and
Se--Se Tetradentates) 40, optionally having halogen or polarizing
or water-insolubilizing/solubilizing groups attached. Ligand can
also contain nonbinding N, O, S, or P atoms. Se Valence Stabilizer
#18: RR'N.sup.+.dbd.C(SeH)(SeH), where R and R' Diselenocarbamates,
represent H, OH, SH, OR'' (R'' = C.sub.1-C.sub.30 alkyl or
Bis(diselenocarbamates), and aryl), SR'' (R'' = C.sub.1-C.sub.30
alkyl or aryl), NH.sub.2 or Poly(diselenocarbamates) (including N-
any organic functional group wherein the hydroxydiselenocarbamates
and N- number of carbon atoms ranges from 0 to 40,
mercaptodiselenocarbamates) (Se--Se optionally having halogen or
polarizing or Bidentates, Se--Se Tridentates, and Se--Se
water-insolubilizing/solubilizing groups Tetradentates) attached.
Ligand can also contain nonbinding N, O, S, or P atoms. Se Valence
Stabilizer #19: (O.dbd.)P(--Se--R)(--Se--R')(--Se--R'') or
(Se.dbd.)P(--Se-- Triselenophosphoric Acids R)(--Se--R')(--O--R''),
where R, R', and R'' (Phosphorotriselenoic Acids), represent H,
NH.sub.2 or any organic functional Bis(triselenophosphoric acids),
group wherein the number of carbon atoms Poly(triselenophosphoric
acids), and ranges from 0 to 40, optionally having halogen
derivatives thereof (Se--Se Bidentates, or polarizing or water-
Se--Se Tridentates, Se--Se Tetradentates)
insolubilizing/solubilizing groups attached. Ligand can also
contain nonbinding N, O, S, or P atoms. Se Valence Stabilizer #20:
(O.dbd.)P(--Se--R)(--Se--R')(--O--R'') or (Se.dbd.)P(--Se--
Diselenophosphoric Acids R)(--O--R')(--O--R''), where R, R', and
R'' (Phosphorodiselenoic Acids), represent H, NH.sub.2 or any
organic functional Bis(diselenophosphoric acids), group wherein the
number of carbon atoms Poly(diselenophosphoric acids), and ranges
from 0 to 40, optionally having halogen derivatives thereof (Se--Se
Bidentates, or polarizing or water- Se--Se Tridentates, Se--Se
Tetradentates) insolubilizing/solubilizing groups attached. Ligand
can also contain nonbinding N, O, S, or P atoms. Se Valence
Stabilizer #21: (Se.dbd.)P(--Se--R)(--Se--R')(--Se--R''), where
R, R', Tetraselenophosphoric Acids and R'' represent H, NH.sub.2 or
any organic (Phosphorotetraselenoic Acids), functional group
wherein the number of carbon Bis(tetraselenophosphoric acids),
atoms ranges from 0 to 40, optionally having
Poly(tetraselenophosphoric acids), and halogen or polarizing or
water- derivatives thereof (Se--Se Bidentates,
insolubilizing/solubilizing groups attached. Se--Se Tridentates,
Se--Se Tetradentates) Ligand can also contain nonbinding N, O, S,
or P atoms. Se Valence Stabilizer #22: R--Se--C(.dbd.Se)--O--R' or
R--Se--C(.dbd.O)--Se--R' for Diselenocarbonates,
Triselenocarbonates, diselenocarbonates, and
R--Se--C(.dbd.Se)--Se--R' for Bis(diselenocarbonates), and
triselenocarbonates, where R, and R' represent
Bis(triselenocarbonates), (Se--Se Bidentates H, NH.sub.2 or any
organic functional group wherein and Se--Se Tetradentates) the
number of carbon atoms ranges from 0 to 40, optionally having
halogen or polarizing or water-insolubilizing/solubilizing groups
attached. Ligand can also contain nonbinding N, O, S, or P atoms.
Se Valence Stabilizer #23: Selenocyanates bound directly to the
high Selenocyanates (Se Monodentates) valence metal ion. Se Valence
Stabilizer #24: Selenolates (HSe--R, HSe--R--SeH, etc.), where R
Selenolates (Se Monodentates) and R' represent H or any organic
functional group wherein the number of carbon atoms ranges from 0
to 35, optionally having halogen or polarizing or water-
insolubilizing/solubilizing groups attached. Miscellaneous Valence
Stabilizer #1: Dialkenes or bicyclic or tricyclic hydrocarbons
Diene or bicyclic or tricyclic hydrocarbon bound directly to the
high valence metal ion. ligands Miscellaneous Valence Stabilizer
#2: Cyanide and cyanate and related ligands bound Cyanide and
related ligands directly to the high valence metal ion.
Miscellaneous Valence Stabilizer #3: Carbonyl (--CO) ligands bound
directly to the Carbonyl ligands high valence metal ion.
Miscellaneous Valence Stabilizer #4: Halogen (X) atoms bound
directly to the high Halogen ligands valence metal ion.
Miscellaneous Valence Stabilizer #5: Hydroxo and oxo ligands bound
directly to the Hydroxo and Oxo Ligands high valence metal ion.
N Valence Stabilizer #1a: Examples of five-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all binding sites
are composed of nitrogen (usually amine or imine groups) and are
not contained in component heterocyclic rings (N--N Tridentates or
N--N Tetradentates) that meet the requirements for use as "narrow
band" valence stabilizers for Co.sup.+3 include, but are not
limited to: pentaazacyclodecane ([10]aneN.sub.5);
pentaazacycloundecane ([11]aneN.sub.5); pentaazacyclododecane
([12]aneN.sub.5); pentaazacyclotridecane ([13]aneN.sub.5);
pentazaacyclotetradecane ([14]aneN.sub.5); pentaazacyclopentadecane
([15]aneN.sub.5); pentaazacyclodecatriene ([10]trieneN.sub.5);
pentaazacycloundecatriene ([11]trieneN.sub.5);
pentaazacyclododecatriene ([12]trieneN.sub.5);
pentaazacyclotridecatriene ([13]trieneN.sub.5);
pentazaacyclotetradecatriene ([14]trieneN.sub.5); and
pentaazacyclopentadecatriene ([15]trieneN.sub.5). N Valence
Stabilizer #1b: Examples of seven-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all binding sites
are composed of nitrogen (usually amine or imine groups) and are
not contained in component heterocyclic rings (N--N Tridentates,
N--N Tetradentates, or N--N Hexadentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: heptaazacyclotetradecane
([14]aneN.sub.7); heptaazacyclopentadecane ([15]aneN.sub.7);
heptaazacyclohexadecane ([16]aneN.sub.7); heptaazacycloheptadecane
([17]aneN.sub.7); heptaazacyclooctadecane ([18]aneN.sub.7);
heptaazacyclononadecane ([19]aneN.sub.7); heptaazacycloeicosane
([20]aneN.sub.7); heptaazacycloheneicosane ([21]aneN.sub.7);
heptaazacyclotetradecatriene ([14]trieneN.sub.7);
heptaazacyclopentadecatriene ([15]trieneN.sub.7);
heptaazacyclohexadecatriene ([16]trieneN.sub.7);
heptaazacycloheptadecatriene ([17]trieneN.sub.7);
heptaazacyclooctadecatriene ([18]trieneN.sub.7);
heptaazacyclononadecatriene ([19]trieneN.sub.7);
heptaazacycloeicosatriene ([20]trieneN.sub.7); and
heptaazacycloheneicosatriene ([21]trieneN.sub.7). N Valence
Stabilizer #1c: Examples of nine-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all binding sites
are composed of nitrogen (usually amine or imine groups) and are
not contained in component heterocyclic rings (N--N Tridentates,
N--N Tetradentates, or N--N Hexadentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: nonaazacyclooctadecane
([18]aneN.sub.9); nonaazacyclononadecane ([19]aneN.sub.9);
nonaazacycloeicosane ([20]aneN.sub.9); nonaazacycloheneicosane
([21]aneN.sub.9); nonaazacyclodocosane ([22]aneN.sub.9);
nonaazacyclotricosane ([23]aneN.sub.9); nonaazacyclotetracosane
([24]aneN.sub.9); nonaazacyclopentacosane ([25]aneN.sub.9);
nonaazacyclohexacosane ([26]aneN.sub.9); nonaazacycloheptacosane
([27]aneN.sub.9); nonaazacyclooctadecatetradiene
([18]tetradieneN.sub.9); nonaazacyclononadecatetradiene
([19]tetradieneN.sub.9); nonaazacycloeicosatetradiene
([20]tetradieneN.sub.9); nonaazacycloheneicosatetradiene
([21]tetradieneN.sub.9); nonaazacyclodocosatetradiene
([22]tetradieneN.sub.9); nonaazacyclotricosatetradiene
([23]tetradieneN.sub.9); nonaazacyclotetracosatetradiene
([24]tetradieneN.sub.9); nonaazacyclopentacosatetradiene
([25]tetradieneN.sub.9); nonaazacyclohexacosatetradiene
([26]tetradieneN.sub.9); and nonaazacycloheptacosatetradiene
([27]tetradieneN.sub.9). N Valence Stabilizer #2a: Examples of
five-membered macrocyclics, macrobicyclics, and macropolycyclics
(including catapinands, cryptands, cyclidenes, and sepulchrates)
wherein all five binding sites are composed of nitrogen and are
contained in component 5-membered heterocyclic rings (N--N
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
pentaphyrins (pentapyrroles); sapphyrins; smaragdyrins;
pentaoxazoles; pentaisooxazoles; pentathiazoles; pentaisothiazoles;
pentaazaphospholes; pentaimidazoles; pentapyrazoles;
pentaoxadiazoles; pentathiadiazoles; pentadiazaphospholes;
pentatriazoles; pentaoxatriazoles; and pentathiatriazoles. N
Valence Stabilizer #2b: Examples of seven-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all seven binding
sites are composed of nitrogen and are contained in component
5-membered heterocyclic rings (N--N Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: heptaphyrins
(heptapyrroles); heptaoxazoles; heptaisooxazoles; heptathiazoles;
heptaisothiazoles; heptaazaphospholes; heptaimidazoles;
heptapyrazoles; heptaoxadiazoles; heptathiadiazoles;
heptadiazaphospholes; heptatriazoles; heptaoxatriazoles; and
heptathiatriazoles. N Valence Stabilizer #3a: Examples of
five-membered macrocyclics, macrobicyclics, and macropolycyclics
(including catapinands, cryptands, cyclidenes, and sepulchrates)
wherein all five binding sites are composed of nitrogen and are
contained in a combination of 5-membered heterocyclic rings and
amine or imine groups (N--N Tridentates or N--N Tetradentates) that
meet the requirements for use as "narrow band" valence stabilizers
for Co.sup.+3 include, but are not limited to: superphthalocyanine;
supernaphthalocyanine; diazapentaphyrins; tetraazapentaphyrins;
pentaazapentaphyrins; diazapentapyrazoles; tetraazapentapyrazoles;
pentaazapentapyrazoles; diazapentaimidazoles;
tetraazapentaimidazoles; and pentaazapentaimidazoles. N Valence
Stabilizer #3b: Examples of seven-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all seven binding
sites are composed of nitrogen and are contained in a combination
of 5-membered heterocyclic rings and amine or imine groups (N--N
Tridentates, N--N Tetradentates, or N--N Hexadentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: diazaheptaphyrins;
tetraazaheptaphyrins; hexaazaheptaphyrins; diazaheptapyrazoles;
tetraazaheptapyrazoles; hexaazaheptapyrazoles;
diazaheptaimidazoles; tetraazaheptaimidazoles; and
hexaazaheptaimidazoles. N Valence Stabilizer #3c: Examples of
nine-membered macrocyclics, macrobicyclics, and macropolycyclics
(including catapinands, cryptands, cyclidenes, and sepulchrates)
wherein all nine binding sites are composed of nitrogen and are
contained in a combination of 5-membered heterocyclic rings and
amine or imine groups (N--N Tridentates, N--N Tetradentates, or
N--N Hexadentates) that meet the requirements for use as "narrow
band" valence stabilizers for Co.sup.+3 include, but are not
limited to: diazanonaphyrins; tetraazanonaphyrins;
hexaazanonaphyrins; diazanonapyrazoles; tetraazanonapyrazoles;
hexaazanonapyrazoles; diazanonaimidazoles; tetraazanonaimidazoles;
and hexaazanonaimidazoles. N Valence Stabilizer #4a: Examples of
five-membered macrocyclics, macrobicyclics, and macropolycyclics
(including catapinands, cryptands, cyclidenes, and sepulchrates)
wherein all five binding sites are composed of nitrogen and are
contained in component 6-membered heterocyclic rings (N--N
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
cyclopentapyridines; cyclopentaoxazines; cyclopentathiazines;
cyclopentaphosphorins; cyclopentaquinolines; cyclopentapyrazines;
cyclopentapyridazines; cyclopentapyrimidines;
cyclopentaoxadiazines; cyclopentathiadiazines;
cyclopentadiazaphosphorins cyclopentaquinoxalines;
cyclopentatriazines; cyclopentathiatriazines; and
cyclopentaoxatriazines. N Valence Stabilizer #4b: Examples of
seven-membered macrocyclics, macrobicyclics, and macropolycyclics
(including catapinands, cryptands, cyclidenes, and sepulchrates)
wherein all seven binding sites are composed of nitrogen and are
contained in component 6-membered heterocyclic rings (N--N
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
cycloheptapyridines; cycloheptaoxazines; cycloheptathiazines;
cycloheptaphosphorins; cycloheptaquinolines; cycloheptapyrazines;
cycloheptapyridazines; cycloheptapyrimidines;
cycloheptaoxadiazines; cycloheptathiadiazines;
cycloheptadiazaphosphorins cycloheptaquinoxalines;
cycloheptatriazines; cycloheptathiatriazines; and
cycloheptaoxatriazines. N Valence Stabilizer #5a: Examples of
five-membered macrocyclics, macrobicyclics, and macropolycyclics
(including catapinands, cryptands, cyclidenes, and sepulchrates)
wherein all five binding sites are composed of nitrogen and are
contained in a combination of 6-membered heterocyclic rings and
amine or imine groups (N--N Tridentates or N--N Tetradentates) that
meet the requirements for use as "narrow band" valence stabilizers
for Co.sup.+3 include, but are not limited to:
diazacyclopentapyridines; tetraazacyclopentapyridines;
diazacyclopentaquinolines; tetraazacyclopentaquinolines;
diazacyclopentapyrazines; tetraazacyclopentapyrazines;
diazacyclopentapyridazines; tetraazacyclopentapyridazines;
diazacyclopentapyrimidines; tctraazacyclopentapyrimidines;
diazacyclopentatriazines; and tetraazacyclopentatriazines. N
Valence Stabilizer #5b: Examples of seven-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all seven binding
sites are composed of nitrogen and are contained in a combination
of 6-membered heterocyclic rings and amine or imine groups (N--N
Tridentates, N--N Tetradentates, or N--N Hexadentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to:
diazacycloheptapyridines; tetraazacycloheptapyridines;
diazacycloheptaquinolines; tetraazacycloheptaquinolines;
diazacycloheptapyrazines; tetraazacycloheptapyrazines;
diazacycloheptapyridazines; tetraazacycloheptapyridazines;
diazacycloheptapyrimidines; tetraazacycloheptapyrimidines;
diazacycloheptatriazines; and tetraazacycloheptatriazines. N
Valence Stabilizer #5c: Examples of nine-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all nine binding
sites are composed of nitrogen and are contained in a combination
of 6-membered heterocyclic rings and amine or imine groups (N--N
Tridentates, N--N Tetradentates, or N--N Hexadentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: diazacyclononapyridines;
tetraazacyclononapyridines; diazacyclononaquinolines;
tetraazacyclononaquinolines; diazacyclononapyrazines;
tctraazacyclononapyrazines; diazacyclononapyridazines;
tetraazacyclononapyridazines; diazacyclononapyrimidines;
tetraazacyclononapyrimidines; diazacyclononatriazines; and
tetraazacyclononatriazines. N Valence Stabilizer #6: Examples
ofsilylamines and silazanes (N Monodentates, N--N Bidentates, N--N
Tridentates, N--N Tetradentates, and N--N Hexadentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: trisilylamine;
N-methyldisilazane (disilylmethylamine); N,N-dimethylsilylamine;
(silyldimethylamine); tris(trimethylsilyl)amine; triethylsilylamine
(triethylaminosilane) (triethylsilazane); N-ethyltriethylsilylamine
(triethyl-N-ethylaminosilane); di-tert-butylsilanediamine
(di-tert-butyldiaminosilane); bis(methylamino)diethylsilane;
tris(dimethylamino)ethylsilane; hexamethyldisilazane;
N-methylhexaphenyldisilazane; hexamethylcyclotrisilazane; and
octaphenylcyclotetrasilazane. [Note: Silylamines and silazanes are
notably weaker ligands than their carbonaceous derivatives,
although replacement of one or two SiR.sub.3 groups with CR.sub.3
will enhance the donor power of the ligand. Thus,
N(CR.sub.3).sub.2(SiR.sub.3) is a better ligand than
N(CR.sub.3)(SiR.sub.3).sub.2, etc.] N Valence Stabilizer #7:
Examples of guanidines, diguanidines, and polyguanidines (N--N
bidentates, N--N tridentates, N--N tetradentates, and N--N
hexadentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
guanidine; methylguanidine; ethylguanidine; isopropylguanidine;
butylguanidine; benzylguanidine; phenylguanidine; tolylguanidine;
naphthylguanidine; cyclohexylguanidine; norbornylguanidine;
adamantylguanidine; dimethylguanidine; diethylguanidine;
diisopropylguanidine; dibutylguanidine; dibenzylguanidine;
diphenylguanidine; ditolylguanidine; dinaphthylguanidine;
dicyclohexylguanidine; dinorbornylguanidine; diadamantylguanidine;
ethylenediguanidine; propylenediguanidine;
tetramethylenediguanidine; pentamethylenediguanidine;
hexamethylenediguanidine; heptamethylenediguanidine;
octamethylenediguanidine; phenylenediguanidine;
piperazinediguanidine; oxalyldiguanidine; malonyldiguanidine;
succinyldiguanidine; glutaryldiguanidine; adipyldiguanidine;
pimelyldiguanidine; suberyldiguanidine; phthalyldiguanidine;
benzimidazoleguanidine; aminoguanidine; nitroaminoguanidine;
dicyandiamide (cyanoguanidine); dodecylguanidine; and nitrovin. N
Valence Stabilizer #8: Examples of phosphonitrile amides and
bis(phosphonitrile amides) (N--N Bidentates and N--N Tetradentates)
that meet the requirements for use as "narrow band" valence
stabilizers for Co.sup.+3 include, but are not limited to:
phosphononitrile amide; N-phenylphosphonitrile amide;
N-benzylphosphonitrile amide; N-cyclohexylphosphonitrile amide;
N-norbornylphosphonitrile amide; N,N'-diphenylphosphonitrile amide;
N,N'-dibenzylphosphonitrile amide; N,N'-dicyclohexylphosphonitrile
amide; and N,N'-dinorbornylphosphonitrile amide. [Note: The
phosphite (P.sup.+3) valence of the phosphorus atom makes
stabilizization of high valence metal ions much more difficult,
though still possible.] N Valence Stabilizer #9: Examples of
phosphonimidic diamides, bis(phosphonimidic diamides), and
poly(phosphonimidic diamides) (N--N bidentates and N--N
tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
phosphonimidic diamide; N-benzylphosphonimidic diamide;
N-phenylphosphonimidic diamide; N-cyclohexylphosphonimidic diamide;
N-norbornylphosphonimidic diamide; N,N-dibenzylphosphonimidic
diamide; N,N-diphenylphosphonimidic diamide;
N,N-dicyclohexylphosphonimidic diamide; and
N,N-dinorbornylphosphonimidic diamide. [Note: The phosphite
(P.sup.+3) valence of the phosphorus atom makes stabilizization of
high valence metal ions much more difficult, though still
possible.] N Valence Stabilizer#10: Examples ofphosphonamidimidic
acid, phosphonamidimidothioic acid, bis(phosphonamidimidic acid),
bis(phosphonamidimidothioic acid), poly(phosphonamidimidic acid),
poly(phosphonamidimidothioic acid), and derivatives thereof (N--N
Bidentates, and N--N Tetradentates) that meet the requirements for
use as "narrow band" valence stabilizers for Co.sup.+3 include, but
are not limited to: phosphonamidimidic acid,
phosphonamidimidothioic acid; O-phenylphosphonamidimidic acid;
O-benzylphosphonamidimidic acid; O-cyclohexylphosphonamidimidic
acid; O-norbornylphosphonamidimidic acid;
S-phenylphosphonamidimidothioic acid;
S-benzylphosphonamidimidothioic acid;
S-cyclohexylphosphonamidimidothioic acid; and
S-norbornylphosphonamidimidothioic acid. [Note: The phosphite
(P.sup.+3) valence of the phosphorus atom makes stabilizization of
high valence metal ions much more difficult, though still
possible.] N Valence Stabilizer #11: Examples of pyridinaldimines,
bis(pyridinaldimines), and poly(pyridinaldimines) (N--N Bidentates,
N--N Tridentates, and N--N Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: pyridylideneaniline
[N-(pyridylmethylene)benzenamine]; and
(2-pyridyl)benzylideneaniline. N Valence Stabilizer #12: Examples
of hydrazones, bis(hydrazones), and poly(hydrazones) (N
Monodentates, N--N Bidentates, N--N Tridentates, and N--N
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3
include, but are not limited to: acetaldehyde hydrazone;
acetaldehyde phenylhydrazone; acetone hydrazone; acetone
phenylhydrazone; pinacolone hydrazone; pinacolone phenylhydrazone;
benzaldehyde hydrazone; benzaldehyde phenylhydrazone;
naphthaldehyde hydrazone; naphthaldehyde phenylhydrazone;
norbornanone hydrazone; norbornanone phenylhydrazone; camphor
hydrazone; camphor phenylhydrazone; nopinone hydrazone; nopinone
phenylhydrazine; 2-pyridinaldehyde hydrazone; 2-pyridinealdehyde
phenylhydrazone; salicylaldehyde hydrazone; salicylaldehyde
phenylhydrazone; quinolinaldehyde hydrazone; quinolinaldehyde
phenylhydrazone; isatin dihydrazone; isatin di(phenylhydrazone);
camphorquinone dihydrazone; camphorquinone di(phenylhydrazone); and
2-hydrazinobenzimidazole hydrazone. N Valence Stabilizer #13:
Examples of azo compounds without chelate substitution at the
ortho- (for aryl) or alpha- or beta- (for alkyl) positions, bis(azo
compounds), or poly(azo compounds) (N Monodentates, N--N
Bidentates, or N--N Tridentates) that meet the requirements for use
as "narrow band" valence stabilizers for Co.sup.+3 include, but are
not limited to: azobenzene (diphenyldiazene); p-diaminoazobenzene;
p-dimethylaminoazobenzene (butter yellow); methyl orange; Fast
Garnet GBC (4'-amino-2,3'-dimethylazobenzene)[Note: non-bonding
methyl group in the o-position.]; and Alizarin Yellow R. [Note: Azo
compounds without chelate substitution at the ortho- (for aryl) or
beta- (for alkyl) positions tend to stabilize lower oxidation
states in metal ions.] N Valence Stabilizer #14: Examples of
formazans, bis(formazans), and poly(fonmazans) without
ortho-hydroxy, carboxy, thiol, mercapto, amino, or hydrazido
substitution (N--N Bidentates, N--N Tetradentates, and N--N
Hexadentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
1,3,5-triphenylformazan; and 1,3,5-naphthylformazan. N Valence
Stabilizer #15: Examples of hydramides (N--N Bidentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: hydrobenzamide;
hydronaphthamide; and hydrosalicylamide. N Valence Stabilizer #16:
Examples of azines (including ketazines), bis(azines), and
poly(azines) without ortho-hydroxy, carboxy, thiol, mercapto,
amino, or hydrazido substitution (N--N Bidentates, N--N
Tetradentates, and N--N Hexadentates) that meet the requirements
for use as "narrow band" valence stabilizers for Co.sup.+3 include,
but are not limited to: benzalazine; naphthalazine;
cyclohexanonazine; and norbomonazine. N Valence Stabilizer #17:
Examples of Schiff Bases with one Imine (C.dbd.N) Group and without
ortho- (for aryl constituents) or alpha- or beta- (for alkyl
constituents) hydroxy, carboxy, carbonyl, thiol, mercapto,
thiocarbonyl, amino, imino, oximo, diazeno, or hydrazido
substitution (N Monodentates) that meet the requirements for use as
"narrow band" valence stabilizers for Co.sup.+3 include, but are
not limited to: N-(Benzaldehydo)isopropylamine;
N-(Naphthaldehydo)isopropylamine; N-(Acetophenono)isopropylamine;
N-(Propiophenono)isopropylamine; N-(Benzaldehydo)cyclohexylamine;
N-(Naphthaldehydo)cyclohexylamine; N-(Acetophenono)cyclohexylamine;
N-(Propiophenono)cyclohexylamine; N-(Benzaldehydo)aniline (BAAN);
N-(Naphthaldehydo)aniline; N-(Acetophenono)aniline;
N-(Propiophenono)aniline; N-(Benzaldehydo)aminonorbornane;
N-(Naphthaldehydo)aminonorbornane; N-(Acetophenono)aminonorbornane;
N-(Propiophenono)aminonorbornane; (Vanillino)anisidine;
(Cinnamaldehydo)anisidine; N-(o-carboxycinnamaldehydo)aniline;
N-(cinnamaldehydo)aniline; N-(cinnamaldehydo)m- or p-anisidine; and
N-(o-carboxycinnamaldehydo)m- or p-anisidine. N Valence Stabilizer
#18: Examples of isocyanide and cyanamide and related ligands (N
Monodentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
isocyanate (--NCO); isothiocyanate (--NCS); isoselenocyanate
(--NCSe); and cyanamide (--NCN). [Note: the nitrogen atom is
directly complexed to the high valence metal ion.] N Valence
Stabilizer #19: Examples of nitrosyls and nitrites and related
ligands (N Monodentates) that meet the requirements for use as
"narrow band" valence stabilizers for Co.sup.+3 include, but are
not limited to: nitrosyl (--NO); thionitrosyl (--NS); nitrite
(--NO.sub.2); thionitrite (sulfinylamide)(thiazate)(--NSO);
nitrosamine (.dbd.NN.dbd.O); thionitrosamine (.dbd.NN.dbd.S);
nitramine (.dbd.NNO.sub.2); and thionitramine (.dbd.NNS.sub.2)
ligands. N Valence Stabilizer #20: Examples of nitrites,
dinitriles, and polynitriles (N Monodentates, N--N Bidentates, N--N
Tridentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
benzonitrile; naphthonitrile; cyanonaphthalene; cyclohexyl nitrile;
cyanopyridine; cyanopurine; cyanophenol; cyanothiophenol;
adamantane nitrite; norbornyl nitrile; cinnamonitrile;
dicyanobenzene; dicyanobutene; dicyanoimidazole; dicyanopyridine;
cyanotolunitrile; tetracyanoethylene (TCNE);
tetracyanoquinodimethane (TCNQ); diethylaminopropionitrile (deapn),
and polyacrylonitriles. N Valence Stabilizer #21: Examples of azide
ligands (N monodentates) that meet the requirements for use as
"narrow band" valence stabilizers for Co.sup.+3 include, but are
not limited to: azide (--N.sub.3) ions; methyl azide; ethyl azide;
phenyl azide; diphenyltriazene; and phenyl sulfonyl azide. S
Valence Stabilizer #1: Examples of monothioethers (S monodentates)
that meet the requirements for use as "narrow band" valence
stabilizers for Co.sup.+3 include, but are not limited to: hydrogen
sulfide, dimethyl sulfide, diethyl sulfide, dioctyl sulfide,
diphenyl sulfide, dicyclohexyl sulfide, tetramethylene sulfide
(tetrahydrothiophene, tht), trimethylene sulfide, dimethylene
sulfide (ethylene sulfide), pentamethylene sulfide, 1,4-thioxane,
oxathiolane, cyclohexene sulfide, cyclooctene sulfide,
benzotetrahydrothiophene, dibenzothiophene,
naphthotetrahydrothiophene, and thiabicycloheptane. S Valence
Stabilizer #2: Examples of disulfides (S monodentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: methyl disulfide, ethyl
disulfide, phenyl disulfide, nitrophenide, and
1,2-dithiacyclohexane. S Valence Stabilizer #3: Examples of
dithioethers (S monodentates or S--S bidentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: 1,3-dithiane,
1,4-dithiane, benzodithiane, dibenzodithiane, naphthodithiane,
2,5-dithiahexane (dth); 3,6-dithiaoctane (dto);
2,5-dimethyl-3,6-dithiaoctane; 3,7-dithianonane; 2,6-dithiaheptane;
1,6-diphenyl-2,5-dithiahexane; 1,4-diphenyl-1,4-dithiabutane;
1,3-dithiolane; 1,4-dithiane (1,4-dithiacyclohexane);
1,4-dithiacycloheptane (dtch); 1,5-dithiacyclooctane (dtco);
o-phenylenebis(2-thiapropane); o-phenylenebis(2-thiabutane);
2,2'-(thiamethyl)biphenyl, and 2,2'-(thiaethyl)biphenyl. S Valence
Stabilizer #4: Examples of trithioethers (S monodentates, S--S
bidentates, or S--S tridentates) that meet the requirements for use
as "narrow band" valence stabilizers for Co.sup.+3 include, but are
not limited to: 1,3,5-trithiane; 1,3,5-tris(methylthia)cyclohexane;
1,3,5-tris(ethyltbia)cyclohexane;
1,3,5-tris(phenylthia)cyclohexane; 2,5,8-tritbianonane;
3,6,9-trithiaundecane; and 2,6,10-trithiaundecane. S Valence
Stabilizer #5: Examples of tetrathioethers (S monodentates, S--S
bidentates, S--S tridentates, or S--S tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to:
1,4,10,13-tetrathiatridecane; 2,6,10,14-tetrathiapentadecane;
2,5,8,11-tetrathiadodecane; 2,5,9,12-ttetrathiatridecane;
2,6,9,13-tetrathiatetradecane;
1,4-(o-thiomethyl)phenyl-1,4-dithiabutane;
1,5-(o-thiomethyl)phenyl-1,5-dithiapentane;
1,6-(o-thiomethyl)phenyl-1,6-dithiahexane;
1,4-(o-thiomethyl)phenyl-1,4-dithiabut-2-ene; and polythioethers. S
Valence Stabilizer #6: Examples of hexathioethers (S monodentates,
S--S bidentates, S--S tridentates, S--S tetradentates, or S--S
hexadentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
tri(2-((o-thiomethyl)phenyl)ethyl)amine; and
tri((o-thiomethyl)phenyl)methylamine. S Valence Stabilizer #7a:
Examples of 5-membered heterocyclic rings containing one sulfur
atom (S monodentates) that meet the requirements for use as "narrow
band" valence stabilizers for Co.sup.+3 include, but are not
limited to: dihydrothiophene, thiophene, thiazole, thiapyrroline,
thiaphospholene, thiaphosphole, oxathiole, thiadiazole,
thiatriazole, benzodihydrothiophene, benzothiophene, benzothiazole,
benzothiaphosphole, dibenzothiophene, and naphthothiophene. S
Valence Stabilizer #7b: Examples of 5-membered heterocyclic rings
containing two sulfur atoms (S monodentates or S--S bidentates)
that meet the requirements for use as "narrow band" valence
stabilizers for Co.sup.+3 include, but are not limited to:
dithiole, benzodithiole, and naphthodithiole. S Valence Stabilizer
#8a: Examples of 6-membered heterocyclic rings containing one
sulfur atom (S monodentates) that meet the requirements for use as
"narrow band" valence stabilizers for Co.sup.+3 include, but are
not limited to: dihydrothiopyran, thiopyran, thiazine, thiadiazine,
thiaphosphorin, thiadiphosphorin, oxathiin, benzothiopyran,
dibenzothiopyran, and naphthothiopyran. S Valence Stabilizer #8b:
Examples of 6-membered hetero cyclic rings containing two sulfur
atoms (S monodentates or S--S bidentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: dihydrodithlim, dithuin,
benzodithimn, dibenzodithiin (thianthrene), and naphthodithiin. S
Valence Stabilizer #9a: Examples of 5-membered heterocyclic rings
containing one sulfur atom and having at least one additional
sulfur atom binding site not contained in a ring (S Monodentates,
S--S Bidentates, S--S Tridentates, S--S Tetradentates, or S--S
Hexadentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
2,5-dimercapto-2,5-dihydrothiophene;
2,5-bis(thiomethyl)-2,5-dihydrothiophene;
2,5-bis(2-thiophenyl)-2,5-dihydrothiophene;
2,5-dimercaptothiophene; 2,5-bis(thiomethyl)thiophene;
2,5-bis(2-thiophenyl)thiophene; 2,5-dimercatothiazoic;
2,5-bis(thiomethyl)thiazole; 2,5-bis(2-thiophenyl)thiazole;
2,5-dimercapto-1,3,4-thiadiazole [bismuththiol];
2-mercaptothianaphthene; 7-(thiomethyl)thianaphthene;
1,8-dimercaptodibenzothiophene; 2-mercaptobenzothiazole;
2-mercapro-1,3,4-thiadiazole; 2-amino-5-mercapto-1,3,4-thiadiazole;
2,5-bis(alkylthio)-1,3,4-thiadiazole; and
7-(thiomethyl)benzothiazole. S Valence Stabilizer #9b: Examples of
5-membered heterocyclic rings containing two sulfur atoms and
having at least one additional sulfur atom binding site not
contained in a ring (S Monodentates, S--S Bidentates, S--S
Tridentates, S--S Tetradentates, or S--S Hexadentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: 2-mercapto-1,3-dithiole;
2-(dimercaptomethyl)-1,3-dithiole; 4,5-dimercapto-1,3-dithiole;
4,5-bis(2-thiophenyl)-1,3-dithiole; 2-mercaptobenzodithiole; and
7-mercaptob enzodithiole. S Valence Stabilizer #10a: Examples of
6-membered heterocyclic rings containing one sulfur atom and having
at least one additional sulfur atom binding site not contained in a
ring (S Monodentates, S--S Bidentates, S--S Tridentates, S--S
Tetradentates, or S--S Hexadentates) that meet the requirements for
use as "narrow band" valence stabilizers for Co.sup.+3 include, but
are not limited to: 2,6-dimercapto-2,5-dihydrothiopyran;
2,6-bis(thiomethyl)-2,5-dihydrothiopyran;
2,6-bis(2-thiophenyl)-2,5-dihydrothiopyran;
2,6-dimercaptothiopyran; 2,6-bis(thiomethyl)thiopyran;
2,6-bis(2-thiophenyl)thiopyran; 2,6-dimercaptothiazine;
2,6-bis(thiomethyl)thiazine; 2,6-bis(2-thiophenyl)thiazine;
2,6-dimercapto-1,3,5-thiadiazine; 2-mercapto-1-benzothiopyran;
8-mercapto-1-benzothiopyran; and 1,9-dimercaptodibenzothiopyran. S
Valence Stabilizer #10b: Examples of 6-membered heterocyclic rings
containing two sulfur atoms and having at least one additional
sulfur atom binding site not contained in a ring (S Monodentates,
S--S Bidentates, S--S Tridentates, S--S Tetradentates, or S--S
Hexadentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
2-mercapto-1,4-dithiin; 2,6-dimercapto-1,4-dithiin;
2,6-bis(2-thiophenyl)-1,4-dithiin; 2,3-dimercapto-1,4-benzodithiin;
5,8-dimercapto-1,4-benzodithiin; 1,8-dimercaptothianthrene; and
1,4,5,8-tetramercaptothianthrene. S Valence Stabilizer #11a:
Examples of 5-membered heterocyclic rings containing one sulfur
atom and having at least one additional sulfur atom binding site
contained in a ring (S Monodentates, S--S Bidentates, S--S
Tridentates, S--S Tetradentates) that meet the requirements for use
as "narrow band" valence stabilizers for Co.sup.+3 include, but are
not limited to: 2,2'-bi-2,5-dihydrothiophene;
2,2',2''-tri-2,5-dihydrothiophene; 2,2'-bithiophene;
2,2',2''-trithiophene; 2,2'-bithiazole; 5,5'-bithiazole;
2,2'-bioxathiole; 2,2'-bi-1,3,4-thiadiazole; 2,2'-bithianaphthene;
2,2'-bibenzothiazole; 1,1'-bis(dibenzothiophene); and
polythiophenes. S Valence Stabilizer #11b: Examples of 5-membered
heterocyclic rings containing two sulfur atoms and having at least
one additional sulfur atom binding site contained in a ring (S
Monodentates, S--S Bidentates, S--S Tridentates, S--S
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
2,2'-bi-1,3-dithiole; 4,4'-bi-1,3-dithiole;
7,7'-bi-1,2-benzodithiole; 3,3'-bi-1,2-benzodithiole; and
tetrathiofulvalene. S Valence Stabilizer #12a: Examples
of6-membered heterocyclic rings containing one sulfur atom and
having at least one additional sulfur atom binding site contained
in a ring (S Monodentates, S--S Bidentates, S--S Tridentates, S--S
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
2,2'-bi-2,5-dihydrothiopyran; 2,2',2''-tri-2,5-dihydrothiopyran;
2,2'-bithiopyran; 2,2',2''-trithiopyran; 2,2'-bi-1,4-thiazine;
2,2'-bi-1,3,5-thiadiazine; 2,2'-bi-1-benzothiopyran; and
1,1'-bis(dibenzothiopyran) S Valence Stabilizer #12b: Examples of
6-membered heterocyclic rings containing two sulfur atoms and
having at least one additional sulfur atom binding site contained
in a ring (S Monodentates, S--S Bidentates, S--S Tridentates, S--S
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
2,2'-bi-1,4-dithiin; 2,2'-bi-1,3-dithiin; 5,5'-bi-1,4-benzodithiin;
2,2'-bi-1,3-benzodithiin; and 1,1'-bithianthrene. S Valence
Stabilizer #13a: Examples of two-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein both binding sites
are composed of sulfur (usually thiol or thioether groups) and are
not contained in component heterocyclic rings (S--S Bidentates)
that meet the requirements for use as "narrow band" valence
stabilizers for Co.sup.+3 include, but are not limited to:
dithiacyclobutane ([4]aneS.sub.2); dithiacyclopentane
([5]aneS.sub.2); dithiacyclohexane ([6]aneS.sub.2);
dithiacycloheptane ([7]aneS.sub.2); dithiacyclooctane
([8]aneS.sub.2); dithiacyclobutene ([4]eneS.sub.2);
dithiacyclopentene ([5]eneS.sub.2); dithiacyclohexene
([6]eneS.sub.2); dithiacycloheptene ([7]eneS.sub.2);
dithiacyclooctene ([8]eneS.sub.2); dithiacyclobutadiene
([4]dieneS.sub.2); dithiacyclopentadiene ([5]dieneS.sub.2);
dithiacyclohexadiene ([6]dieneS.sub.2); dithiacycloheptadiene
([7]dieneS.sub.2); and dithiacyclooctadiene ([8]dieneS.sub.2). S
Valence Stabilizer #13b: Examples of three-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all binding sites
are composed of sulfur (usually thiol or thioether groups) and are
not contained in component heterocyclic rings (S--S Tridentates)
that meet the requirements for use as "narrow band" valence
stabilizers for Co.sup.+3 include, but are not limited to:
trithiacyclohexane ([6]aneS.sub.3); trithiacycloheptane
([7]aneS.sub.3); trithiacyclooctane ([8]aneS.sub.3);
trithiacyclononane ([9]aneS.sub.3) trithiacyclodecane
([10]aneS.sub.3); trithiacycloundecane ([11]aneS.sub.3);
trithiacyclododecane ([12]aneS.sub.3);
trithiacyclohexene ([6]eneS.sub.3); trithiacycloheptene
([7]eneS.sub.3); trithiacyclooctene ([8]eneS.sub.3)
trithiacyclononene ([9]eneS.sub.3); trithiacyclodecene
([10]eneS.sub.3); trithiacycloundecene ([11]eneS.sub.3);
trithiacyclododecene ([12]eneS.sub.3); trithiacyclohexatriene
([6]trieneS.sub.3); trithiacycloheptatriene ([7]trieneS.sub.3);
trithiacyclooctatriene ([8]trieneS.sub.3); trithiacyclononatriene
([9]trieneS.sub.3); trithiacyclodecatriene ([10]trieneS.sub.3);
trithiacycloundecatriene ([11]trieneS.sub.3); and
trithiacyclododecatriene ([12]trieneS.sub.3). S Valence Stabilizer
#13c: Examples of four-membered macrocyclics, macrobicyclics, and
macropolycyclics (including catapinands, cryptands, cyclidenes, and
sepulchrates) wherein all binding sites are composed of sulfur
(usually thiol or thioether groups) and are not contained in
component heterocyclic rings (S--S Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: tetrathiacyclooctane
([8]aneS.sub.4); tetrathiacyclononane ([9]aneS.sub.4);
tetrathiacyclodecane ([10]aneS.sub.4); tetrathiacycloundecane
([11]aneS.sub.4); tetrathiacyclododecane ([12]aneS.sub.4);
tetrathiacyclotridecane ([13]aneS.sub.4); tetrathiacyclotetradecane
([14]aneS.sub.4); tetrathiacyclopentadecane ([15]aneS.sub.4);
tetrathiacyclohexadecane ([16]aneS.sub.4);
tetrathiacycloheptadecane ([17]aneS.sub.4);
tetrathiacyclooctadecane ([18]aneS.sub.4); tetrathiacyclononadecane
([19]aneS.sub.4); tetrathiacycloeicosane ([20]aneS.sub.4);
tetrathiacyclooctadiene ([8]dieneS.sub.4); tetrathiacyclononadiene
([9]dieneS.sub.4); tetrathiacyclodecadiene ([10]dieneS.sub.4);
tetrathiacycloundecadiene ([11]dieneS.sub.4);
tetrathiacyclododecadiene ([12]dieneS.sub.4);
tetrathiacyclotridecadiene ([13]dieneS.sub.4);
tetrathiacyclotetradecadiene ([14]dieneS.sub.4);
tetrathiacyclopentadecadiene ([15]dieneS.sub.4);
tetrathiacyclohexadecadiene ([16]dieneS.sub.4);
tetrathiacycloheptadecadiene ([17]dieneS.sub.4);
tetrathiacyclooctadecadiene ([18]dieneS.sub.4);
tetrathiacyclononadecadiene ([19]dieneS.sub.4);
tetrathiacycloeicosadiene ([20]dieneS.sub.4);
tetrathiacyclooctatetradiene ([8]tetradieneS.sub.4);
tetrathiacyclononatetradiene ([9]tetradieneS.sub.4);
tetrathiacyclodecatetradiene ([10]tetradieneS.sub.4);
tetrathiacycloundecatetradiene ([11]tetradieneS.sub.4);
tetrathiacyclododecatetradiene ([12]tetradieneS.sub.4);
tetrathiacyclotridecatetradi ene ([13]tetradieneS.sub.4);
tetrathiacyclotetradecatetradiene ([14]tetradieneS.sub.4);
tetrathiacyclopentadecatetradiene ([15]tetradieneS.sub.4);
tetrathiacyclohexadecatetradiene ([16]tetradieneS.sub.4);
tetrathiacycloheptadecatetradiene ([17]tetradieneS.sub.4);
tetrathiacyclooctadecatetradiene ([18]tetradieneS.sub.4);
tetrathiacyclononadecatetradiene ([19]tetradieneS.sub.4); and
tetrathiacycloeicosatetradiene ([20]tetradieneS.sub.4). S Valence
Stabilizer #13d: Examples of five-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all binding sites
are composed of sulfur (usually thiol or thioether groups) and are
not contained in component heterocyclic rings (S--S Tridentates or
S--S Tetradentates) that meet the requirements for use as "narrow
band" valence stabilizers for Co.sup.+3 include, but are not
limited to: pentathiacyclodecane ([10]aneS.sub.5);
pentathiacycloundecane ([11]aneS.sub.5); pentathiacyclododecane
([12]aneS.sub.5); pentathiacyclotridecane ([13]anes.sub.5);
pentathiacyclotetradecane ([14]aneS.sub.5);
pentathiacyclopentadecane ([15]aneS.sub.5);
pentathiacyclodecatriene ([10]trieneS.sub.5);
pentathiacycloundecatriene ([11]trieneS.sub.5);
pentathiacyclododecatriene ([12]trieneS.sub.5);
pentathiacyclotridecatriene ([13]trieneS.sub.5);
pentathiacyclotetradecatriene ([14]trieneS.sub.5); and
pentathiacyclopentadecatriene ([15]trieneS.sub.5). S Valence
Stabilizer #13e: Examples of six-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all binding sites
are composed of sulfur (usually thiol or thioether groups) and are
not contained in component heterocyclic rings (S--S Tridentates,
S--S Tetradentates, or S--S Hexadentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: hexathiacyclododecane
([12]aneS.sub.6); hexathiacyclotridecane ([13]aneS.sub.6);
hexathiacyclotetradecane ([14]aneS.sub.6); hexathiacyclopentadecane
([15]aneS.sub.6); hexathiacyclohexadecane ([16]aneS.sub.6);
hexathiacycloheptadecane ([17]aneS.sub.6); hexathiacyclooctadecane
([18]aneS.sub.6); hexathiacyclononadecane ([19]aneS.sub.6);
hexathiacycloeicosane ([20]aneS.sub.6); hexathiacycloheneicosane
([21]aneS.sub.6); hexathiacyclodocosane ([22]aneS.sub.6);
hexathiacyclotricosane ([23]aneS.sub.6); hexathiacyclotetracosane
([24]aneS.sub.6); hexathiacyclododecatriene ([12]trieneS.sub.6);
hexathiacyclotridecatriene ([13]trieneS.sub.6);
hexathiacyclotetradecatriene ([14]trieneS.sub.6);
hexathiacyclopentadecatriene ([15]trieneS.sub.6);
hexathiacyclohexadecatriene ([16]trieneS.sub.6);
hexathiacycloheptadecatriene ([17]trieneS.sub.6);
hexathiacyclooctadecatriene ([18]trieneS.sub.6);
hexathiacyclononadecatriene ([19]trieneS.sub.6);
hexathiacycloeicosatriene ([20]trieneS.sub.6);
hexathiacycloheneicosatriene ([21]trieneS.sub.6);
hexathiacyclodocosatriene ([22]trieneS.sub.6);
hexathiacyclotricosatriene ([23]trieneS.sub.6); and
hexathiacyclotetracosatriene ([24]trieneS.sub.6). S Valence
Stabilizer #13f: Examples of seven-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all binding sites
are composed of sulfur (usually thiol or thioether groups) and are
not contained in component heterocyclic rings (S--S Tridentates,
S--S Tetradentates, or S--S Hexadentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to:
heptathiacyclotetradecane ([14]aneS.sub.7);
heptathiacyclopentadecane ([15]aneS.sub.7);
heptathiacyclohexadecane ([16]aneS.sub.7);
heptathiacycloheptadecane ([17]aneS.sub.7);
heptathiacyclooctadecane ([18]aneS.sub.7); heptathiacyclononadecane
([19]aneS.sub.7); heptathiacycloeicosane ([20]aneS.sub.7);
heptathiacycloheneicosane ([21]aneS.sub.7);
heptathiacyclotetradecatriene ([14]trieneS.sub.7);
heptathiacyclopentadecatriene ([15]trieneS.sub.7);
heptathiacyclohexadecatriene ([16]trieneS.sub.7);
heptathiacycloheptadecatriene ([17]trieneS.sub.7);
heptathiacyclooctadecatriene ([18]trieneS.sub.7);
heptathiacyclononadecatriene ([19]trieneS.sub.7);
heptathiacycloeicosatriene ([20]trieneS.sub.7); and
heptathiacycloheneicosatriene ([21]trieneS.sub.7). S Valence
Stabilizer #13g: Examples of eight-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all binding sites
are composed of sulfur (usually thiol or thioether groups) and are
not contained in component heterocyclic rings (S--S Tridentates,
S--S Tetradentates, or S--S Hexadentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: octathiacyclohexadecane
([16]aneS.sub.8); octathiacycloheptadecane ([17]aneS.sub.8);
octathiacyclooctadecane ([18]aneS.sub.8); octathiacyclononadecane
([19]aneS.sub.8); octathiacycloeicosane ([20]aneS.sub.8);
octathiacycloheneicosane ([21]aneS.sub.8); octathiacyclodocosane
([22]aneS.sub.8); octathiacyclotricosane ([23]aneS.sub.8);
octathiacyclotetracosane ([24]aneS.sub.8);
octathiacyclohexadecatetradiene ([16]tetradieneS.sub.8);
octathiacycloheptadecatetradiene ([17]tetradieneS.sub.8);
octathiacyclooctadecatetradiene ([18]tetradieneS.sub.8);
octathiacyclononadecatetradiene ([19]tetradieneS.sub.8);
octathiacycloeicosatetradiene ([20]tetradieneS.sub.8); o
ctathiacycl ohenei co satetradi ene ([21]tetradieneS.sub.8);
octathiacyclodocosatetradiene ([22]tetradieneS.sub.8);
octathiacyclotricosatetradiene ([23]tetradieneS.sub.8); and
octathiacyclotetracosatetradiene ([24]tetradieneS.sub.8). S Valence
Stabilizer #13h: Examples of nine-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all binding sites
are composed of sulfur (usually thiol or thioether groups) and are
not contained in component heterocyclic rings (S--S Tridentates,
S--S Tetradentates, or S--S Hexadentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: nonathiacyclooctadecane
([18]aneS.sub.9); nonathiacyclononadecane ([19]aneS.sub.9);
nonathiacycloeicosane ([20]aneS.sub.9); nonathiacycloheneicosane
([21]aneS.sub.9); nonathiacyclodocosane ([22]aneS.sub.9);
nonathiacyclotricosane ([23]aneS.sub.9); nonathiacyclotetracosane
([24]aneS.sub.9); nonathiacyclopentacosane ([25]aneS.sub.9);
nonathiacyclohexacosane ([26]aneS.sub.9); nonathiacycloheptacosane
([27]aneS.sub.9); nonathiacyclooctadecatetradiene
([18]tetradieneS.sub.9); nonathiacyclononadecatetradiene
([19]tetradieneS.sub.9); nonathiacycloeicosatetradiene
([20]tetradieneS.sub.9); nonathiacycloheneicosatetradiene
([21]tetradieneS.sub.9); nonathiacyclodocosatetradiene
([22]tetradieneS.sub.9); nonathiacyclotricosatetradiene
([23]tetradieneS.sub.9); nonathiacyclotetracosatetradiene
([24]tetradieneS.sub.9); nonathiacyclopentacosatetradiene
([25]tetradieneS.sub.9); nonathiacyclohexacosatetradiene
([26]tetradieneS.sub.9); and nonathiacycloheptacosatetradiene
([27]tetradieneS.sub.9). S Valence Stabilizer #13i: Examples of
ten-membered macrocyclics, macrobicyclics, and macropolycyclics
(including catapinands, cryptands, cyclidenes, and sepulchrates)
wherein all binding sites are composed of sulfur (usually thiol or
thioether groups) and are not contained in component heterocyclic
rings (S--S Tridentates, S--S Tetradentates, or S--S Hexadentates)
that meet the requirements for use as "narrow band" valence
stabilizers for Co.sup.+3 include, but are not limited to:
decathiacycloeicosane ([20]aneS.sub.10); decathiacycloheneicosane
([21]aneS.sub.10); decathiacyclodocosane ([22]aneS.sub.10);
decathiacyclotricosane ([23]aneS.sub.10); decathiacyclotetracosane
([24]aneS.sub.10); decathiacyclopentacosane ([25]aneS.sub.10);
decathiacyclohexacosane ([26]aneS.sup.10); decathiacycloheptacosane
([27]aneS.sub.10); decathiacyclooctacosane ([28]aneS.sub.10);
decathiacyclononacosane ([29]aneS.sub.10); decathiacyclotriacontane
([30]aneS.sub.10); decathiacyclocicosapentadiene
([20]pentadieneS.sub.10); decathiacycloheneicosapentadiene
([21]pentadieneS.sub.10); decathiacyclodocosapentadiene
([22]pentadieneS.sub.10); decathi acyclotricosapentadiene
([23]pentadieneS.sub.10); decathiacyclotetracosapentadiene
([24]pentadieneS.sub.10); decathiacyclopentacosapentadiene
([25]pentadieneS.sub.10); decathiacyclohexacosapentadiene
([26]pentadieneS.sub.10); decathiacycloheptacosapentadiene
([27]pentadieneS.sub.10); decathiacyclooctacosapentadiene
([28]pentadieneS.sub.10); decathiacyclononacosapentadiene
([29]pentadieneS.sub.10); and decathiacyclotriacontapentadiene
([30]pentadieneS.sub.10). S Valence Stabilizer #14a: Examples of
four-membered macrocyclics, macrobicyclics, and macropolycyclics
(including catapinands, cryptands, cyclidenes, and sepulchrates)
wherein all four binding sites are composed of sulfur and are
contained in component 5-membered heterocyclic rings (S--S
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
tetrathiophenes; tetrathiazoles; tetrathiaphospholes;
tetraoxathioles; tetrathiadiazoles; tetrathiatriazoles; and
tetradithioles. S Valence Stabilizer #14b: Examples of
five-membered macrocyclics, macrobicyclics, and macropolycyclics
(including catapinands, cryptands, cyclidenes, and sepulchrates)
wherein all five binding sites are composed of sulfur and are
contained in component 5-membered heterocyclic rings (S--S
Tridentates or S--S Tetradentates) that meet the requirements for
use as "narrow band" valence stabilizers for Co.sup.+3 include, but
are not limited to: pentathiophenes; pentathiazoles;
pentathiaphospholes; pentaoxathioles; pentathiadiazoles;
pentathiatriazoles; and pentadithioles. S Valence Stabilizer #14c:
Examples of six-membered macrocyclics, macrobicyclics, and
macropolycyclics (including catapinands, cryptands, cyclidenes, and
sepulchrates) wherein all six binding sites are composed of sulfur
and are contained in component 5-membered heterocyclic rings (S--S
Tridentates, S--S Tetradentates, or S--S Hexadentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: hexathiophenes;
hexathiazoles; hexathiaphospholes; hexaoxathioles;
hexathiadiazoles; hexathiatriazoles; and hexadithioles. S Valence
Stabilizer #14d: Examples of seven-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all seven binding
sites are composed of sulfur and are contained in component
5-membered heterocyclic rings (S--S Tridentates, S--S
Tetradentates, or S--S Hexadentates) that meet the requirements for
use as "narrow band" valence stabilizers for Co.sup.+3 include, but
are not limited to: heptathiophenes; heptathiazoles;
heptathiaphospholes; heptaoxathioles; heptathiadiazoles;
heptathiatriazoles; and heptadithioles. S Valence Stabilizer #14e:
Examples of eight-membered macrocyclics, macrobicyclics, and
macropolycyclics(including catapinands, cryptands, cyclidenes, and
sepulchrates) wherein all eight binding sites are composed of
sulfur and are contained in component 5-membered heterocyclic rings
(S--S Tridentates, S--S Tetradentates, or S--S Hexadentates) that
meet the requirements for use as "narrow band" valence stabilizers
for Co.sup.+3 include, but are not limited to: octathiophenes;
octathiazoles; octathiaphospholes; octaoxathioles;
octathiadiazoles; octathiatriazoles; and octadithioles. S Valence
Stabilizer #14f: Examples of nine-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all nine binding
sites are composed of sulfur and are contained in component
5-membered heterocyclic rings (S--S Tridentates, S--S
Tetradentates, or S--S Hexadentates) that meet the requirements for
use as "narrow band" valence stabilizers for Co.sup.+3 include, but
are not limited to: nonathiophenes; nonathiazoles;
nonathiaphospholes; nonaoxathioles; nonathiadiazoles;
nonathiatriazoles; and nonadithioles. S Valence Stabilizer #14g:
Examples of ten-membered macrocyclics, macrobicyclics, and
macropolycyclics (including catapinands, cryptands, cyclidenes, and
sepulchrates) wherein all ten binding sites are composed of sulfur
and are contained in component 5-membered heterocyclic rings (S--S
Tridentates, S--S Tetradentates, or S--S Hexadentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: decathiophenes;
decathiazoles; decathiaphospholes; decaoxathioles;
decathiadiazoles; decathiatriazoles; and decadithioles. S Valence
Stabilizer #15a: Examples of four-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all four binding
sites are composed of sulfur and are contained in a combination of
5-membered heterocyclic rings and thiol, thioether, or thioketo
groups (S--S Tetradentates) that meet the requirements for use as
"narrow band" valence stabilizers for Co.sup.+3 include, but are
not limited to: dithiatetrathiophenes; tetrathiatetrathiophenes;
dithiatetradithioles; and tetrathiatetradithioles. S Valence
Stabilizer #15b: Examples of
five-membered macrocyclics, macrobicyclics, and macropolycyclics
(including catapinands, cryptands, cyclidenes, and sepulchrates)
wherein all five binding sites are composed of sulfur and are
contained in a combination of 5-membered heterocyclic rings and
thiol, thioether, or thioketo groups (S--S Tridentates or S--S
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
dithiapentathiophenes; tetrathiapentathiophenes;
dithiapentadithioles; and tetrathiapentadithioles. S Valence
Stabilizer #15c: Examples of six-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all six binding
sites are composed of sulfur and are contained in a combination of
5-membered heterocyclic rings and thiol, thioether, or thioketo
groups (S--S Tridentates, S--S Tetradentates, or S--S Hexadentates)
that meet the requirements for use as "narrow band" valence
stabilizers for Co.sup.+3 include, but are not limited to:
dithiahexaathiophenes; trithiahexathiophenes; dithiahexadithioles;
and trithiahexadithioles. S Valence Stabilizer #15d: Examples of
seven-membered macrocyclics, macrobicyclics, and macropolycyclics
(including catapinands, cryptands, cyclidenes, and sepulchrates)
wherein all seven binding sites are composed of sulfur and are
contained in a combination of 5-membered heterocyclic rings and
thiol, thioether, or thioketo groups (S--S Tridentates, S--S
Tetradentates, or S--S Hexadentates) that meet the requirements for
use as "wide band" valence stabilizers for Co.sup.+3 include, but
are not limited to: dithiaheptathiophenes;
tetrathiaheptathiophenes; dithiaheptadithioles; and
tetrathiaheptadithioles. S Valence Stabilizer #15e: Examples of
eight-membered macrocyclics, macrobicyclics, and macropolycyclics
(including catapinands, cryptands, cyclidenes, and sepulchrates)
wherein all eight binding sites are composed of sulfur and are
contained in a combination of 5-membered heterocyclic rings and
thiol, thioether, or thioketo groups (S--S Tridentates, S--S
Tetradentates, or S--S Hexadentates) that meet the requirements for
use as "narrow band" valence stabilizers for Co.sup.+3 include, but
are not limited to: dithiaoctathiophenes; tetrathiaoctathiophenes;
dithiaoctadithioles; and tetrathiaoctadithioles. S Valence
Stabilizer #15f: Examples of nine-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all nine binding
sites are composed of sulfur and are contained in a combination of
5-membered heterocyclic rings and thiol, thioether, or thioketo
groups (S--S Tridentates, S--S Tetradentates, or S--S Hexadentates)
that meet the requirements for use as "narrow band" valence
stabilizers for Co.sup.+3 include, but are not limited to:
trithianonathiophenes; hexathianonathiophenes;
trithianonadithioles; and hexathianonadithioles. S Valence
Stabilizer #15g: Examples of ten-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all ten binding
sites are composed of sulfur and are contained in a combination of
5-membered heterocyclic rings and thiol, thioether, or thioketo
groups (S--S Tridentates, S--S Tetradentates, or S--S Hexadentates)
that meet the requirements for use as "narrow band" valence
stabilizers for Co.sup.+3 include, but are not limited to:
dithiadecathiophenes; pentathiadecathiophenes; dithiadecadithioles;
and pentathiadecadithioles. S Valence Stabilizer #16a: Examples of
four-membered macrocyclics, macrobicyclics, and macropolycyclics
(including catapinands, cryptands, cyclidenes, and sepulchrates)
wherein all four binding sites are composed of sulfur and are
contained in component 6-membered heterocyclic rings (S--S
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
tetrathiopyrans; tetrathiazines; tetrathiaphosphorins;
tetrathiadiphosphorins; tetraoxathiins; and tetradithiins. S
Valence Stabilizer #16b: Examples of five-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all five binding
sites are composed of sulfur and are contained in component
6-membered heterocyclic rings (S--S Tridentates or S--S
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
pentathiopyrans; pentathiazines; pentathiaphosphorins;
pentathiadiphosphorins; pentaoxathiins; and pentadithiins. S
Valence Stabilizer #16c: Examples of six-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all six binding
sites are composed of sulfur and are contained in component
6-membered heterocyclic rings (S--S Tridentates, S--S
Tetradentates, or S--S Hexadentates) that meet the requirements for
use as "narrow band" valence stabilizers for Co.sup.+3 include, but
are not limited to: hexathiopyrans; hexathiazines;
hexathiaphosphorins; hexathiadiphosphorins; hexaoxathiins; and
hexadithiins. S Valence Stabilizer #16d: Examples of seven-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
seven binding sites are composed of sulfur and are contained in
component 6-membered heterocyclic rings (S--S Tridentates, S--S
Tetradentates, or S--S Hexadentates) that meet the requirements for
use as "narrow band" valence stabilizers for Co.sup.+3 include, but
are not limited to: heptathiopyrans; heptathiazines;
heptathiaphosphorins; heptathiadiphosphorins; heptaoxathiins; and
heptadithiins. S Valence Stabilizer #16e: Examples of
eight-membered macrocyclics, macrobicyclics, and macropolycyclics
(including catapinands, cryptands, cyclidenes, and sepulchrates)
wherein all eight binding sites are composed of sulfur and are
contained in component 6-membered heterocyclic rings (S--S
Tridentates, S--S Tetradentates, or S--S Hexadentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: octathiopyrans;
octathiazines; octathiaphosphorins; octathiadiphosphorins;
octaoxathiins; and octadithiins. S Valence Stabilizer #16f:
Examples of nine-membered macrocyclics, macrobicyclics, and
macropolycyclics (including catapinands, cryptands, cyclidenes, and
sepulchrates) wherein all nine binding sites are composed of sulfur
and are contained in component 6-membered heterocyclic rings (S--S
Tridentates, S--S Tetradentates, or S--S Hexadentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: nonathiopyrans;
nonathiazines; nonathiaphosphorins; nonathiadiphosphorins;
nonaoxathiins; and nonadithiins. S Valence Stabilizer #16g:
Examples of ten-membered macrocyclics, macrobicyclics, and
macropolycyclics (including catapinands, cryptands, cyclidenes, and
sepulchrates) wherein all ten binding sites are composed of sulfur
and are contained in component 6-membered heterocyclic rings (S--S
Tridentates, S--S Tetradentates, or S--S Hexadentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: decathiopyrans;
decathiazines; decathiaphosphorins; decathiadiphosphorins;
decaoxathiins; and decadithiins. S Valence Stabilizer #17a:
Examples of four-membered macrocyclics, macrobicyclics, and
macropolycyclics (including catapinands, cryptands, cyclidenes, and
sepulchrates) wherein all four binding sites are composed of sulfur
and are contained in a combination of 6-membered heterocyclic rings
and thiol, thioether, or thioketo groups (S--S Tetradentates) that
meet the requirements for use as "narrow band" valence stabilizers
for Co.sup.+3 include, but are not limited to:
dithiatetrathiopyrans; tetrathiatetrathiopyrans;
dithiatetrathiazines; tetrathiatetrathiazines;
dithiatetrathiaphosphorins; tetrathiatetrathiaphosphorins;
dithiatetraoxathiins; tetrathiatetraoxathiins; dithiatetradithiins;
and tetrathiatetradithiins. S Valence Stabilizer #17b: Examples of
five-membered macrocyclics, macrobicyclics, and macropolycyclics
(including catapinands, cryptands, cyclidenes, and sepulchrates)
wherein all five binding sites are composed of sulfur and are
contained in a combination of 6-membered heterocyclic rings and
thiol, thioether, or thioketo groups (S--S Tridentates or S--S
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
dithiapentathiopyrans; tetrathiapentathiopyrans;
dithiapentathiazines; tetrathiapentathiazines;
dithiapentathiaphosphorins; tetrathiapentathiaphosphorins;
dithiapentaoxathiins; tetrathiapentaoxathiins; dithiapentadithiins;
and tetrathiapentadithiins. S Valence Stabilizer #17c: Examples of
six-membered macrocyclics, macrobicyclics, and macropolycyclics
(including catapinands, cryptands, cyclidenes, and sepulchrates)
wherein all six binding sites are composed of sulfur and are
contained in a combination of 6-membered heterocyclic rings and
thiol, thioether, or thioketo groups (S--S Tridentates, S--S
Tetradentates, or S--S Hexadentates) that meet the requirements for
use as "narrow band" valence stabilizers for Co.sup.+3 include, but
are not limited to: dithiahexathiopyrans; trithiahexathiopyrans;
dithiahexathiazines; trithiahexathiazines;
dithiahexathiaphosphorins; trithiahexathiaphosphorins;
dithiahexaoxathiins; trithiahexaoxathiins; dithiahexadithiins; and
trithiahexadithiins. S Valence Stabilizer #17d: Examples of
seven-membered macrocyclics, macrobicyclics, and macropolycyclics
(including catapinands, cryptands, cyclidenes, and sepulchrates)
wherein all seven binding sites are composed of sulfur and are
contained in a combination of 6-membered heterocyclic rings and
thiol, thioether, or thioketo groups (S--S Tridentates, S--S
Tetradentates, or S--S Hexadentates) that meet the requirements for
use as "narrow band" valence stabilizers for Co.sup.+3 include, but
are not limited to: dithiaheptathiopyrans;
tetrathiaheptathiopyrans; dithiaheptathiazines;
tetrathiaheptathiazines; dithiaheptathiaphosphorins;
tetrathiaheptathiaphosphorins; dithiaheptaoxathiins;
tetrathiaheptaoxathiins; dithiaheptadithiins; and
tetrathiaheptadithiins. S Valence Stabilizer #17e: Examples of
eight-membered macrocyclics, macrobicyclics, and macropolycyclics
(including catapinands, cryptands, cyclidenes, and sepulchrates)
wherein all eight binding sites are composed of sulfur and are
contained in a combination of 6-membered heterocyclic rings and
thiol, thioether, or thioketo groups (S--S Tridentates, S--S
Tetradentates, or S--S Hexadentates) that meet the requirements for
use as "narrow band" valence stabilizers for Co.sup.+3 include, but
are not limited to: dithiaoctathiopyrans; tetrathiaoctathiopyrans;
dithiaoctathiazines; tetrathiaoctathiazines;
dithiaoctathiaphosphorins; tetrathiaoctathiaphosphorins;
dithiaoctaoxathiins; tetrathiaoctaoxathiins; dithiaoctadithiins;
and tetrathiaoctadithiins. S Valence Stabilizer #17f: Examples of
nine-membered macrocyclics, macrobicyclics, and macropolycyclics
(including catapinands, cryptands, cyclidenes, and sepulchrates)
wherein all nine binding sites are composed of sulfur and are
contained in a combination of 6-membered heterocyclic rings and
thiol, thioether, or thioketo groups (S--S Tridentates, S--S
Tetradentates, or S--S Hexadentates) that meet the requirements for
use as "narrow band" valence stabilizers for Co.sup.+3 include, but
are not limited to: trithianonathiopyrans; hexathianonathiopyrans;
trithianonathiazines; hexathianonathiazines;
trithianonathiaphosphorins; hexathianonathiaphosphorins;
trithianonaoxathiins; hexathianonaoxathiins; trithianonadithiins;
and hexathianonadithiins. S Valence Stabilizer #17g: Examples of
ten-membered macrocyclics, macrobicyclics, and macropolycyclics
(including catapinands, cryptands, cyclidenes, and sepulchrates)
wherein all ten binding sites are composed of sulfur and are
contained in a combination of 6-membered heterocyclic rings and
thiol, thioether, or thioketo groups (S--S Tridentates, S--S
Tetradentates, or S--S Hexadentates) that meet the requirements for
use as "narrow band" valence stabilizers for Co.sup.+3 include, but
are not limited to: dithiadecathiopyrans; pentathiadecathiopyrans;
dithiadecathiazines; pentathiadecathiazines;
dithiadecathiaphosphorins; pentathiadecathiaphosphorins;
dithiadecaoxathiins; pentathiadecaoxathiins; dithiadecadithiins;
and pentathiadecadithiins. S Valence Stabilizer #18: Examples of
dithiobiurets (dithioimidodicarbonic diamides), dithioisobiurets,
dithiobiureas, trithiotriurets, trithiotriureas,
bis(dithiobiurets), bis(dithioisobiurets), bis(dithiobiureas),
poly(dithiobiurets), poly(dithioisobiurets), and
poly(dithiobiureas) (S--S Bidentates, S--S Tridentates, S--S
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
dithiobiuret, dithioisobiuret, dithiobiurea, trithiotriuret,
trithiotriurea, nitrodithiobiuret, dinitrodithiobiuret,
aminodithiobiuret, diaminodithiobiuret, oxydithiobiuret,
dioxydithiobiuret, cyanodithiobiuret, methyldithiobiuret,
ethyldithiobiuret, isopropyldithiobiuret, phenyldithiobiuret,
benzyldithiobiuret, cyclohexyldithiobiuret, norbornyldithiobiuret,
adamantyldithiobiuret, dimethyldithiobiuret, diethyldithiobiuret,
diisopropyldithiobiuret, diphenyldithiobiuret,
dibenzyldithiobiuret, dicyclohexyldithiobiuret,
dinorbornyldithiobiuret, and diadamantyldithiobiuret. S Valence
Stabilizer #19: Examples ofthioacylthioureas, thioaroylthioureas,
bis(thioacylthioureas), bis(thioaroylthioureas),
poly(thioacylthioureas), and poly(thioaroylthioureas) (S--S
Bidentates, S--S Tridentates, S--S Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: thioformylthiourea,
thioacetylthiourea, thiobenzoylthiourea, thiocyclohexoylthiourea,
pentafluorothiobenzoylthiourea, N-methylthioacetylthiourea,
N-phenylthiobenzoylthiourea, and
N-cyclohexylthiocyclohexoylthiourea. S Valence Stabilizer #20:
Examples of dithioacyl disulfides, bis(dithioacyl disulfides), and
poly(dithioacyl disulfides), (S--S Bidentates, S--S Tridentates,
S--S Tetradentates) that meet the requirements for use as "narrow
band" valence stabilizers for Co.sup.+3 include, but are not
limited to: dithioacetyl disulfide; dithiopropanoyl disulfide;
dithiobenzoyl disulfide; and dithiopentafluorobenzoyl disulfide. S
Valence Stabilizer #21: Examples of tetrathioperoxydicarbonic
diamides, bis(tetrathioperoxydicarbonic diamides), and
poly(tetrathioperoxydicarbonic diamides) (S--S Bidentates, S--S
Tridentates, S--S Tetradentates) that meet the requirements for use
as "narrow band" valence stabilizers for Co.sup.+3 include, but are
not limited to: tetrathioperoxydicarbonic diamide;
N-phenyltetrathioperoxydicarbonic diamide;
N-benzyltetrathioperoxydicarbonic diamide;
N-cyclohexyltetrathioperoxydicarbonic diamide;
N-norbornyltetrathioperoxydicarbonic diamide;
N,N'-diphenyltetrathioperoxydicarbonic diamide;
N,N'-dibenzyltetrathioperoxydicarbonic diamide;
N,N'-dicyclohexyltetrathioperoxydicarbonic diamide; and
N,N'-dinorbornyltetrathioperoxydicarbonic diamide. S Valence
Stabilizer #22: Examples of hexathio-, pentathio-, and
tetrathioperoxydicarbonic acids, bis(hexathio-, pentathio-, and
tetrathioperoxydicarbonic acids), poly(hexathio-, pentathio-, and
tetrathioperoxydicarbonic acids), and derivatives thereof (S--S
Bidentates, S--S Tridentates, S--S Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: hexathioperoxydicarbonic
acid, pentathioperoxydicarbonic acid, tetrathioperoxydicarbonic
acid, S-phenylhexathioperoxydicarbonic acid;
S-benzylhexathioperoxydicarbonic acid;
S-cyclohexylhexathioperoxydicarbonic acid;
S-norbornylhexathioperoxydicarbonic acid;
S,S'-diphenylhexathioperoxydicarbonic acid;
S,S'-dibenzylhexathioperoxydicarbonic acid;
S,S'-dicyclohexylhexathioperoxydicarbonic acid; and
S,S'-dinorbornylhexathioperoxydicarbonic acid. S Valence Stabilizer
#23: Examples of dithioperoxydiphosphoramides,
bis(dithioperoxydiphosphoramides), and
poly(dithioperoxydiphosphoramides) (S--S Bidentates, S--S
Tridentates, S--S Tetradentates) that meet the requirements for use
as "narrow band" valence stabilizers for Co.sup.+3 include, but are
not limited to: dithioperoxydiphosphoramide,
N-methyldithioperoxydiphosphoramide,
N-isopropyldithioperoxydiphosphoramide,
N-tert-butyldithioperoxydiphosphoramide,
N-phenyldithioperoxydiphosphoramide,
N-pentafluorophenyldithioperoxydiphosphoramide,
N-benzyldithioperoxydiphosphoramide,
N-cyclohexyldithioperoxydiphosphoramide,
N-norbornyldithioperoxydiphosphoramide,
N,N'''-dimethyldithioperoxydiphosphoramide,
N,N'''-diisopropyldithioperoxydiphosphoramide,
N,N'''-di-tert-butyldithioperoxydiphosphoramide,
N,N'''-diphenyldithioperoxydiphosphoramide,
N,N'''-di-pentafluorophenyldithioperoxydiphosphoramide,
N,N'''-dibenzyldithioperoxydiphosphoramide, N,N'''-di
cyclohexyldithioperoxydiphosphoramide, and
N,N'''-dinorbornyldithioperoxydiphosphoramide. S Valence Stabilizer
#24: Examples of dithioperoxydiphosphoric acids,
bis(dithioperoxydiphosphoric acids), poly(dithioperoxydiphosphoric
acids), and derivatives thereof (S--S Bidentates, S--S Tridentates,
S--S Tetradentates) that meet the requirements for use as "narrow
band" valence stabilizers for Co.sup.+3 include, but are not
limited to: dithioperoxydiphosphoric acid,
methyldithioperoxydiphosphoric acid,
isopropyldithioperoxydiphosphoric acid,
tert-butyldithioperoxydiphosphoric acid,
phenyldithioperoxydiphosphoric acid,
pentafluorophenyldithioperoxydiphosphoric acid,
benzyldithioperoxydiphosphoric acid,
cyclohexyldithioperoxydiphosphoric acid,
norbornyldithioperoxydiphosphoric acid,
dimethyldithioperoxydiphosphoric acid,
diisopropyldithioperoxydiphosphoric acid,
di-tert-butyldithioperoxydiphosphoric acid,
diphenyldithioperoxydiphosphoric acid,
di-pentafluorophenyldithioperoxydiphosphoric acid,
dibenzyldithioperoxydiphosphoric acid,
dicyclohexyldithioperoxydiphosphoric acid, and
dinorbornyldithioperoxydiphosphoric acid. S Valence Stabilizer #25:
Examples of dithioimidodiphosphonic acids,
dithiohydrazidodiphosphonic acids, bis(dithioimidodiphosphonic
acids), bis(dithiohydrazidodiphosphonic acids),
poly(dithioimidodiphosphonic acids),
poly(dithiohydrazidodiphosphonic acids), and derivatives
thereof(S--S Bidentates, S--S Tridentates, S--S Tetradentates) that
meet the requirements for use as "narrow band" valence stabilizers
for Co.sup.+3 include, but are not limited to:
dithioimidodiphosphonic acid, methyldithioimidodiphosphonic acid,
isopropyldithioimidodiphosphonic acid,
tert-butyldithioimidodiphosphonic acid,
phenyldithioimidodiphosphonic acid,
pentafluorophenyldithioimidodiphosphonic acid,
benzyldithioimidodiphosphonic acid,
cyclohexyldithioimidodiphosphonic acid,
norbornyldithioimidodiphosphonic acid,
dimethyldithioimidodiphosphonic acid,
diisopropyldiothioimidodiphosphonic acid,
di-tert-butyldithioimidodiphosphonic acid,
diphenyldithioimidodiphosphonic acid,
di-pentafluorophenyldithioimidodiphosphonic acid,
dibenzyldithioimidodiphosphonic acid,
dicyclohexyldithioimidodiphosphonic acid, and
dinorbornyldithioimidodiphosphonic acid. [Note: The phosphite
(p.sup.+3) valence of the phosphorus atom makes stabilizization of
high valence metal ions much more difficult, though still
possible.] S Valence Stabilizer #26: Examples of
dithioimidodiphosphonamides, dithiohydrazidodiphosphonamides,
bis(dithioimidodiphosphonamides),
bis(dithiohydrazidodiphosphonamides),
poly(dithioimidodiphosphonamides), and
poly(dithiohydrazidodiphosphonamides) (S--S Bidentates, S--S
Tridentates, S--S Tetradentates) that meet the requirements for use
as "narrow band" valence stabilizers for Co.sup.+3 include, but are
not limited to: dithioimidodiphosphonamide,
N-methyldithioimidodiphosphonamide,
N-isopropyldithioimidodiphosphonamide,
N-tert-butyldithioimidodiphosphonamide,
N-phenyldithioimidodiphosphonamide,
N-pentafluorophenyldithioimidodiphosphonamide,
N-benzyldithioimidodiphosphonamide,
N-cyclohexyldithioimidodiphosphonamide,
N-norbornyldithioimidodiphosphonamide,
N,N'''-dimethyldithioimidodiphosphonamide,
N,N'''-diisopropyldithioimidodiphosphonamide,
N,N'''-di-tert-butyldithioimidodiphosphonamide,
N,N'''-diphenyldithioimidodiphosphonamide,
N,N'''-di-pentafluorophenyldithioimidodiphosphonamide,
N,N'''-dibenzyldithioimidodiphosphonamide,
N,N'''-dicyclohexyldithioimidodiphosphonamide, and
N,N'''-dinorbornyldithioimidodiphosphonamide. [Note: The phosphite
(P.sup.+3) valence of the phosphorus atom makes stabilizization of
high valence metal ions much more difficult, though still
possible.] S Valence Stabilizer #27: Examples
ofdithiodiphosphonamides, bis(dithiodiphosphonamides), and
poly(dithiodiphosphonamides) (S--S Bidentates, S--S Tridentates,
S--S Tetradentates) that meet the requirements for use as "narrow
band" valence stabilizers for Co.sup.+3 include, but are not
limited to: dithiodiphosphonamide, N-methyldithiodiphosphonamide,
N-isopropyldithiodiphosphonamide,
N-tert-butyldithiodiphosphonamide, N-phenyldithiodiphosphonamide,
N-pentafluorophenyldithiodiphosphonamide,
N-benzyldithiodiphosphonamide, N-cyclohexyldithiodiphosphonamide,
N-norbornyldithiodiphosphonamide,
N,N'''-dimethyldithiodiphosphonamide,
N,N'''-diisopropyldithiodiphosphonamide,
N,N'''-di-tert-butyldithiodiphosphonamide,
N,N'''-diphenyldithiodiphosphonamide,
N,N'''-di-pentafluorophenyldithiodiphosphonamide,
N,N'''-dibenzyldithiodiphosphonamide,
N,N'''-dicyclohexyldithiodiphosphonamide, and
N,N'''-dinorbornyldithiodiphosphonamide. [Note: The phosphite
(P.sup.+3) valence of the phosphorus atom makes stabilizization of
high valence metal ions much more difficult, though still
possible.] S Valence Stabilizer #28: Examples of dithiodiphosphonic
acids, bis(dithiodiphosphonic acids), poly(dithiodiphosphonic
acids), and derivatives thereof (S--S Bidentates, S--S Tridentates,
S--S Tetradentates) that meet the requirements for use as "narrow
band" valence stabilizers for Co.sup.+3 include, but are not
limited to: dithiodiphosphonic acid, methyldithiodiphosphonic acid,
isopropyldithiodiphosphonic acid, tert-butyldithiodiphosphonic
acid, phenyldithiodiphosphonic acid,
pentafluorophenyldithiodiphosphonic acid, benzyldithiodiphosphonic
acid, cyclohexyldithiodiphosphonic acid,
norbornyldithiodiphosphonic acid, dimethyldithiodiphosphonic acid,
diisopropyldiothiodiphosphonic acid,
di-tert-butyldithiodiphosphonic acid, diphenyldithiodiphosphonic
acid, di-pentafluorophenyldithiodiphosphonic acid,
dibenzyldithiodiphosphonic acid, dicyclohexyldithiodiphosphonic
acid, and dinorbornyldithiodiphosphonic acid. [Note: The phosphite
(P.sup.+3) valence of the phosphorus atom makes stabilizization of
high valence metal ions much more difficult, though still
possible.] S Valence Stabilizer #29: Examples of
dithioperoxydiphosphonamides, bis(dithioperoxydiphosphonamides),
and poly(dithioperoxydiphosphonamides) (S--S Bidentates, S--S
Tridentates, S--S Tetradentates) that meet the requirements for use
as "narrow band" valence stabilizers for Co.sup.+3 include, but are
not limited to: dithioperoxydiphosphonamide,
N-methyldithioperoxydiphosphonamide,
N-isopropyldithioperoxydiphosphonamide,
N-tert-butyldithioperoxydiphosphonamide,
N-phenyldithioperoxydiphosphonamide,
N-pentafluorophenyldithioperoxydiphosphonamide,
N-benzyldithioperoxydiphosphonamide,
N-cyclohexyldithioperoxydiphosphonamide,
N-norbornyldithioperoxydiphosphonamide,
N,N'''-dimethyldithioperoxydiphosphonamide,
N,N'''-diisopropyldithioperoxydiphosphonamide,
N,N'''-di-tert-butyldithioperoxydiphosphonamide,
N,N'''-diphenyldithioperoxydiphosphonamide,
N,N'''-di-pentafluorophenyldithioperoxydiphosphonamide,
N,N'''-dibenzyldithioperoxydiphosphonamide,
N,N'''-dicyclohexyldithioperoxydiphosphonamide, and
N,N'''-dinorbornyldithioperoxydiphosphonamide. [Note: The phosphite
(P.sup.+3) valence of the phosphorus atom makes stabilizization of
high valence metal ions much more difficult, though still
possible.] S Valence Stabilizer #30: Examples of
dithioperoxydiphosphonic acids, bis(dithioperoxydiphosphonic
acids), poly(dithioperoxydiphosphonic acids), and derivatives
thereof (S--S Bidentates, S--S Tridentates, S--S Tetradentates)
that meet the requirements for use as "narrow band" valence
stabilizers for Co.sup.+3 include, but are not limited to:
dithioperoxydiphosphonic acid, methyldithioperoxydiphosphonic acid,
isopropyldithioperoxydiphosphonic acid,
tert-butyldithioperoxydiphosphonic acid,
phenyldithioperoxydiphosphonic acid,
pentafluorophenyldithioperoxydiphosphonic acid,
benzyldithioperoxydiphosphonic acid,
cyclohexyldithioperoxydiphosphonic acid,
norbornyldithioperoxydiphosphonic acid,
dimethyldithioperoxydiphosphonic acid,
diisopropyldithioperoxydiphosphonic acid,
di-tert-butyldithioperoxydiphosphonic acid,
diphenyldithioperoxydiphosphonic acid,
di-pentafluorophenyldithioperoxydiphosphonic acid,
dibenzyldithioperoxydiphosphonic acid,
dicyclohexyldithioperoxydiphosphonic acid, and
dinorbornyldithioperoxydiphosphonic acid. [Note: The phosphite
(P.sup.+3) valence of the phosphorus atom makes stabilizization of
high valence metal ions much more difficult, though still
possible.] S Valence Stabilizer #31: Examples of dithiophosphonic
acids (phosphonodithioic acids), bis(dithiophosphonic acids),
poly(dithiophosphonic acids), and derivatives thereof(S--S
Bidentates, S--S Tridentates, S--S Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: dithiophosphonic acid,
O-phenyldithiophosphonic acid, O-benzyldithiophosphonic acid,
O-cyclohexyldithiophosphonic acid, O-norbornyldithiophosphonic
acid, O,P-diphenyldithiophosphonic acid,
O,P-dibenzyldithiophosphonic acid, O,P-dicyclohexyldithiophosphonic
acid, and O,P-dinorbornyldithiophosphonic acid. [Note: The
phosphite (P.sup.+3) valence of the phosphorus atom makes
stabilizization of high valence metal ions much more difficult,
though still possible.] S Valence Stabilizer #32: Examples of
trithiophosphonic acids (phosphonotrithioic acids),
bis(trithiophosphonic acids), poly(trithiophosphonic acids), and
derivatives thereof(S--S Bidentates, S--S Tridentates, S--S
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
trithiophosphonic acid, S-phenyltrithiophosphonic acid,
S-benzyltrithiophosphonic acid, S-cyclohexyltrithiophosphonic acid,
S-norbornyltrithiophosphonic acid, S,P-diphenyltrithiophosphonic
acid, S,P-dibenzyltrithiophosphonic acid,
S,P-dicyclohexyltrithiophosphonic acid, and
S,P-dinorbornyltrithiophosphonic acid. [Note: The phosphite
(P.sup.+3) valence of the phosphorus atom makes stabilizization of
high valence metal ions much more difficult, though still
possible.] S Valence Stabilizer #33: Examples of
phosphono(dithioperoxo)thioic acids,
bis[phosphono(dithioperoxo)thioic acids],
poly[phosphono(dithioperoxo)thioic acids], and derivatives thereof
(S--S Bidentates, S--S Tridentates, S--S Tetradentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to:
phosphono(dithioperoxo)thioic acid,
O-phenylphosphono(dithioperoxo)thioic acid,
O-benzylphosphono(dithioperoxo)thioic acid,
O-cyclohexylphosphono(dithioperoxo)thioic acid,
O-norbornylphosphono(dithioperoxo)thioic acid,
O,P-diphenylphosphono(dithioperoxo)thioic acid,
O,P-dibenzylphosphono(dithioperoxo)thioic acid,
O,P-dicyclohexylphosphono(dithioperoxo)thioic acid, and
O,P-dinorbornylphosphono(dithioperoxo)thioic acid. [Note: The
phosphite (P.sup.+3) valence of the phosphorus atom makes
stabilizization of high valence metal ions much more difficult,
though still possible.] S Valence Stabilizer #34: Examples of
phosphono(dithioperoxo)dithioic acids,
bis[phosphono(dithioperoxo)dithioic acids],
poly[phosphono(dithioperoxo)dithioic acids], and derivatives
thereof(S--S Bidentates, S--S Tridentates, S--S Tetradentates) that
meet the requirements for use as "narrow band" valence stabilizers
for Co.sup.+3 include, but are not limited to:
phosphono(dithioperoxo)dithioic acid,
S-phenylphosphono(dithioperoxo)dithioic acid,
S-benzylphosphono(dithioperoxo)dithioic acid,
S-cyclohexylphosphono(dithioperoxo)dithioic acid,
S-norbornylphosphono(dithioperoxo)dithioic acid,
S,P-diphenylphosphono(dithioperoxo)dithioic acid,
S,P-dibenzylphosphono(dithioperoxo)dithioic acid,
S,P-dicyclohexylphosphono(dithioperoxo)dithioic acid, and
S,P-dinorbornylphosphono(dithioperoxo)dithioic acid. [Note: The
phosphite (P.sup.+3) valence of the phosphorus atom makes
stabilizization of high valence metal ions much more difficult,
though still possible.] S Valence Stabilizer #35: Examples of
S-(alkylthio)thiocarboxylic acids, S-(arylthio)thiocarboxylic
acids, and S,S-thiobisthiocarboxylic Acids (S--S Bidentates and
S--S Tridentates) that meet the requirements for use as "narrow
band" valence stabilizers for Co.sup.+3 include, but are not
limited to: (methylthio)thioacetic acid; (methylthio)thiobenzoic
acid; (methylthio)thionicotinic acid; (methylthio)thionapthoic
acid; (phenylthio)thioacetic acid; (phenylthio)thiobenzoic acid;
(phenylthio)thionaphthoic acid; (norbornylthio)thioacetic acid;
(norbornylthio)thiobenzoic acid; (norbornylthio)thionapthoic acid;
thiobisthioacetic acid; thiobisthiobenzoic acid; and
thiobisthionapthoic acid. S Valence Stabilizer #36: Examples of
S-(alkyldisulfido)thiocarboxylic acids,
S-(aryldisulfido)thiocarboxylic acids, and
S,S'-disulfidobisthiocarboxylic acids (S--S Bidentates and S--S
Tridentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
(methyldisulfido)thioacetic acid; (methyldisulfido)thiobenzoic
acid; (methyldisulfido)thionicotinic acid;
(methyldisulfido)thionapthoic acid; (phenyldisulfido)thioacetic
acid; (phenyldisulfido)thiobenzoic acid;
(phenyldisulfido)thionaphthoic acid; (norbornyldisulfido)thioacetic
acid; (norbornyldisulfido)thiobenzoic acid;
(norbornyldisulfido)thionapthoic acid; S,S'-disulfidobisthioacetic
acid; S,S'-disulfidobisthiobenzoic acid; and
S,S'-disulfidobisthionapthoic acid. S Valence Stabilizer #37:
Examples of 1,2-dithiolates, bis(1,2-dithiolates), and
poly(1,2-dithiolates) (S--S Bidentates, S--S Tridentates, S--S
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
2,3-butanedithiol; 1,2-diphenyl-1,2-ethanedithiol;
1,2-di(pentafluorophenyl)-1,2-ethanedithio;
1,2-dicyclohexyl-1,2-ethanedithiol;
1,2-dinorbornyl-1,2-ethanedithiol; 2,3-dimercaptopropanol;
2,3-dimercaptosuccinic acid;
poly[bis(arylthio)acetylene]s; and
poly[bis(alkylylthio)acetylene]s. S Valence Stabilizer #38:
Examples of rhodanines and bis(rhodanines) (S--S Bidentates and
S--S Tetradentates) that meet the requirements for use as "narrow
band" valence stabilizers for Co.sup.+3 include, but are not
limited to: 3-methylrhodanine; 3-ethylrhodanine;
3-isopropylrhodanine; 3-phenylrhodanine; 3-benzylrhodanine;
3-cyclohexylrhodanine; 3-norbornylrhodanine; 5-methylrhodanine;
5-ethylrhodanine; 5-isopropylrhodanine; 5-phenylrhodanine;
5-benzylrhodanine; 5-cyclohexylrhodanine; 5-norbornylrhodanine;
3,3'-ethylenebisrhodanine; 3,3'-propylenerhodanine;
3,3'-butylenerhodanine; 5,5'-ethylenebisrhodanine;
5,5'-propylenerhodanine; and 5,5'-butylenerhodanine. [Note:
rhodanines and bis(rhodanines) tend to stabilize lower oxidation
states in metal ions.] S Valence Stabilizer #39: Examples of
dithiocarbimates, bis(dithiocarbimates), and poly(dithiocarbimates)
(S--S Bidentates, S--S Tridentates, and S--S Tetradentates) that
meet the requirements for use as "narrow band" valence stabilizers
for Co.sup.+3 include, but are not limited to:
methyldithiocarbimate; trifluoromethyldithiocarbimate;
ethyldithiocarbimate; propyldithiocarbimate;
isopropyldithiocarbimate; butyldithiocarbimate;
tertbutyldithiocarbimate; cyanodithiocarbimate (CDC);
cyanamidodithiocarbimate; azidodithiocarbimate;
phenyldithiocarbimate; pentafluorophenyldithiocarbimate;
benzyldithiocarbimate; naphthyldithiocarbimate;
cyclohexyldithiocarbimate; norbornyldithiocarbimate; and
adamantyldithiocarbimate. [Note: Carbimates tend to stabilize lower
oxidation states in metal ions.] S Valence Stabilizer #40: Examples
of thioxanthates, bis(thioxanthates), and poly(thioxanthates) (S--S
Bidentates and S--S Tetradentates) that meet the requirements for
use as "narrow band" valence stabilizers for Co.sup.+3 include, but
are not limited to: methyl thioxanthate (MeSxan); ethyl
thioxanthate (EtSxan); isopropyl thioxanthate (iPrSxan);
trifluoromethyl thioxanthate (CF.sub.3Sxan); cyanothioxanthate;
cyanamidothioxanthate; phenyl thioxanthate (PhSxan); benzyl
thioxanthate (BzSxan); pentafluorophenyl thioxanthate; cyclohexyl
thioxanthate (cHxSxan); and norbornyl thioxanthate. [Note:
Thioxanthates tend to stabilize lower oxidation states in metal
ions.] S Valence Stabilizer #41: Examples of xanthates,
bis(xanthates), and poly(xanthates) (S--S Bidentates and S--S
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
methyl xanthate (Mexan); ethyl xanthate (Etxan); isopropyl xanthate
(iPrxan); trifluoromethyl xanthate (CF.sub.3xan); cyanoxanthate;
cyanamidoxanthate; phenyl xanthate (Phxan); benzyl xanthate
(Bzxan); pentafluorophenyl xanthate; cyclohexyl xanthate (cHxxan);
and norbornyl xanthate. [Note: Xanthates tend to stabilize lower
oxidation states in metal ions.] S Valence Stabilizer #42: Examples
of phosphinodithioformates (S--S Bidentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to:
trimethylphosphinodithioformate; triethylphosphinodithioformate;
triphenylphosphinodithioformate;
tricyclohexylphosphinodithioformate;
dimethylphosphinodithioformate; diethylphosphinodithioformate;
diphenylphosphinodithioformate; and
dicyclohexylphosphinodithioformate. S Valence Stabilizer #43:
Examples of alkyl- and aryl-dithioborates, trithioborates,
perthioborates, bis(dithioborates), bis(trithioborates), and
bis(perthioborates) (S--S Bidentates and S--S Tetradentates) that
meet the requirements for use as "narrow band" valence stabilizers
for Co.sup.+3 include, but are not limited to: S,O-diethyl
dithioborate; S,O-diisopropyl dithioborate; S,O-diphenyl
dithioborate; S,O-dibenzyl dithioborate; S,O-dicyclohexyl
dithioborate; S,O-dinorbornyl dithioborate; diethyl trithioborate;
diisopropyl trithioborate; diphenyl trithioborate; dibenzyl
trithioborate; dicyclohexyl trithioborate; and dinorbornyl
trithioborate. S Valence Stabilizer #44: Examples of alkyl- and
aryl-dithioboronates and bis(dithioboronates) (S--S Bidentates and
S--S Tetradentates) that meet the requirements for use as "narrow
band" valence stabilizers for Co.sup.+3 include, but are not
limited to: diethyl dithioboronate; diisopropyl dithioboronate;
diphenyl dithioboronate; dibenzyl dithioboronate; dicyclohexyl
dithioboronate; and dinorbornyl dithioboronate. [Note: boronates
tend to stabilize lower oxidation states in metal ions.] S Valence
Stabilizer #45: Examples of trithioarsonic acids (arsonotrithioic
acids), dithioarsonic acids (arsonodithioic acids),
tetrathioarsonic acids (arsonotetrathioic acids), and derivatives
thereof (S--S Bidentates, S--S Tridentates, S--S Tetradentates)
that meet the requirements for use as "narrow band" valence
stabilizers for Co.sup.+3 include, but are not limited to:
trithioarsonic acid, O-phenyltrithioarsonic acid,
O-benzyltrithioarsonic acid, O-cyclohexyltrithioarsonic acid,
O-norbornyltrithioarsonic acid, O,S-diphenyltrithioarsonic acid,
O,S-dibenzyltrithioarsonic acid, O,S-dicyclohexyltrithioarsonic
acid, O,S-dinorbornyltrithioarsonic acid; dithioarsonic acid,
O-phenyldithioarsonic acid, O-benzyldithioarsonic acid,
O-cyclohexyldithioarsonic acid, O-norbornyldithioarsonic acid,
O,O-diphenyldithioarsonic acid, O,O-dibenzyldithioarsonic acid,
O,O-dicyclohexyldithioarsonic acid, and
O,O-dinorbornyldithioarsonic acid. S Valence Stabilizer #46:
Examples of trithioantimonic acids (stibonotrithioic acids),
dithioantimonic acids (stibonodithioic acids), tetrathioantimonic
acids (stibonotetrathioic acids), and derivatives thereof (S--S
Bidentates, S--S Tridentates, S--S Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to:
trimethyltrithioantimonate; triethyltrithioantimonate; and
triphenyltrithioantimonate. S Valence Stabilizer #47: Examples of
phosphine P-sulfides and amino-substituted phosphine sulfides (S
Monodentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
trimethylphosphine sulfide (TMPS); triethylphosphine sulfide
(TEPS); triphenylphosphine sulfide (TPhPS); tribenzylphosphine
sulfide (TBzPS); tricyclohexylphosphine sulfide (TcHxPS); and
trinorbornylphosphine sulfide for phosphine P-sulfides; and
tris(dimethylamino)phosphine sulfide; trimorpholinophosphine
sulfide; tripiperidinophosphine sulfide; tripyrrolidinophosphine
sulfide; and tri(cyclohexylamino)phosphine sulfide for
amino-substituted phosphine sulfides. S Valence Stabilizer #48:
Examples of arsine As-sulfides and amino-substituted arsine
sulfides (S Monodentates) that meet the requirements for use as
"narrow band" valence stabilizers for Co.sup.+3 include, but are
not limited to: trimethylarsine sulfide; triethylarsine sulfide;
triphenylarsine sulfide; tribenzylarsine sulfide;
tricyclohexylarsine sulfide; and trinorbornylarsine sulfide for
arsine As-sulfides; and tris(dimethylamino)arsine sulfide;
trimorpholinoarsine sulfide; tripiperidinoarsine sulfide;
tripyrrolidinoarsine sulfide; and tri(cyclohexylamino)arsine
sulfide for amino-substituted arsine sulfides. S Valence Stabilizer
#49: Examples of thiocyanate ligands (S monodentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: selenocyanate (--SCN). S
Valence Stabilizer #50: Examples of thiolates that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: thiophenol;
naphthalenethiol; 1-dodecanethion; hexadecyl mercaptan;
benzenethiol (bt); polybenzenethiols; and polythioarylenes. S
Valence Stabilizer #51: Examples of sulfide that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: sulfides (--S.sup.2-);
disulfides (--S.sub.2.sup.2-); and polysulfides (--S.sub.x.sup.2-).
P Valence Stabilizer #1: Examples of monophosphines (P
monodentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
phosphine, phenylphosphine, diphenylphosphine, triphenylphosphine,
tricyclohexylphosphine, phenyldimethylphosphine,
phenyldiethylphosphine, methyldiphenylphosphine,
ethyldiphenylphosphine, phosphirane, phosphetane, phospholane,
phosphorinane, benzophospholane, benzophosphorinane,
dibenzophospholane, dibenzophosphorinane, naphthophospholane,
naphthophosphorinane, phosphinonorbornane, and phosphinoadamantane.
P Valence Stabilizer #2: Examples of diphosphines (P monodentates
or P--P bidentates) that meet the requirements for use as "narrow
band" valence stabilizers for Co.sup.+3 include, but are not
limited to: diphospholane, benzodiphospholane,
naphthodiphospholane, diphosphorinane, benzodiphosphorinane,
dibenzodiphosphorinane, naphthodiphosphorinane,
bis(diphenylphosphino)methane, bis(diphenylphosphino)ethane,
bis(diphenylphosphino)propane, bis(diphenylphosphino)butane,
bis(diphenylphosphino)pentane, 1,2-bis(diphenylphosphino)ethylene,
and o-phenylenebis(diphenylphosphine). (Note: the aryl derivatives
are air-stable, whereas the alkyl derivatives are air-sensitive and
therefore unsuitable for these applications.) P Valence Stabilizer
#3: Examples of triphosphines (P monodentates, P--P bidentates, or
P--P tridentates) that meet the requirements for use as "narrow
band" valence stabilizers for Co.sup.+3 include, but are not
limited to: triphosphorinane,
P,P'-tetraphenyl-2-methyl-2-(P-diphenyl)phosphinomethyl-1,3-propanediphos-
phine; P,P-[2-(P-diphenyl)phosphinoethyl]diethyl-P-phenylphosphine;
P,P-[2-(P-diphenyl)phosphino]diphenyl-P-phenylphosphine; and
hexahydro-2,4,6-trimethyl-1,3,5-triphosphazine. (Note: the aryl
derivatives are air-stable, whereas the alkyl derivatives are
air-sensitive and therefore unsuitable for these applications.) P
Valence Stabilizer #4: Examples of tetraphosphines (P monodentates,
P--P bidentates, P--P tridentates, and P--P tetradentates) that
meet the requirements for use as "narrow band" valence stabilizers
for Co.sup.+3 include, but are not limited to:
P,P'-tetraphenyl-2,2-[(P-diphenyl)phosphinomethyl]-1,3-propanediphosphine-
; tri[o-(P-diphenyl)phosphinophenyl]phosphine; and
1,1,4,7,10,10-hexaphenyl-1,4,7,10-tetraphosphadecane. (Note: the
aryl derivatives are air-stable, whereas the alkyl derivatives are
air-sensitive and therefore unsuitable for these applications.) P
Valence Stabilizer #5: Examples of pentaphosphines (P monodentates,
P--P bidentates, P--P tridentates, and P--P tetradentates) that
meet the requirements for use as "narrow band" valence stabilizers
for Co.sup.+3 include, but are not limited to:
4-[2-(P-diphenyl)phosphinoethyl]-1,1,7,10,10-pentaphenyl-1,4,7,10-tetraph-
osphadecane. (Note: the aryl derivatives are air-stable, whereas
the alkyl derivatives are air-sensitive and therefore unsuitable
for these applications.) P Valence Stabilizer #6: Examples of
hexaphosphines (P--P bidentates, P--P tridentates, P--P
tetradentates, and P--P hexadentates) that meet the requirements
for use as "narrow band" valence stabilizers for Co.sup.+3 include,
but are not limited to:
1,1,10,10-tetraphenyl-4,7-[2-(P,P-diphenyl)phosphinoethyl]-1,4,7,10-tetra-
phosphadecane. (Note: the aryl derivatives are air-stable, whereas
the alkyl derivatives are air-sensitive and therefore unsuitable
for these applications.) P Valence Stabilizer #7a: Examples of
5-membered heterocyclic rings containing one phosphorus atom (P
monodentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
1-phospholene, 2-phospholene, 3-phospholene, phosphole,
oxaphosphole, thiaphosphole, benzophospholene, benzophosphole,
benzoxaphosphole, benzothiaphosphole, dibenzophospholene,
dibenzophosphole, naphthophospholene, naphthophosphole,
naphthoxaphosphole, naphthothiaphosphole. P Valence Stabilizer #7b:
Examples of 5-membered heterocyclic rings containing two phosphorus
atoms (P monodentates or P--P bidentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: diphospholene,
diphosphole, oxadiphospholene, thiadiphospholene,
benzodiphospholene, benzodiphosphole, naphthodiphospholene, and
naphthodiphosphole. P Valence Stabilizer #7c: Examples of
5-membered heterocyclic rings containing three phosphorus atoms (P
monodentates or P--P bidentates) that meet the requirements for use
as "narrow band" valence stabilizers for Co.sup.+3 include, but are
not limited to: triphosphole. P Valence Stabilizer #8a: Examples of
6-membered heterocyclic rings containing one phosphorus atom (P
monodentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
phosphorin, oxaphosphorin, thiaphosphorin, benzophosphorin,
benzoxaphosphorin, benzothiaphosphorin, acridophosphine,
phosphanthridine, dibenzoxaphosphorin, dibenzothiaphosphorin,
naphthophosphorin, naphthoxaphosphorin, and naphthothiaphosphorin.
P Valence Stabilizer #8b: Examples of 6-membered heterocyclic rings
containing two phosphorus atoms (P monodentates or P--P bidentates)
that meet the requirements for use as "narrow band" valence
stabilizers for Co.sup.+3 include, but are not limited to:
o-diphosphorin, m-diphosphorin, p-diphosphorin, oxadiphosphorin,
thiadiphosphorin, benzodiphosphorin, benzoxadiphosphorin,
benzothiadiphosphorin, dibenzodiphosphorin, dibenzoxadiphosphorin,
dibenzothiadiphosphorin, naphthodiphosphorin,
naphthoxadiphosphorin, and naphthothiadiphosphorin. P Valence
Stabilizer #8c: Examples of 6-membered heterocyclic rings
containing three phosphorus atoms (P monodentates or P--P
bidentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
1,3,5-triphosphorin, 1,2,3-triphosphorin,
benzo-1,2,3-triphosphorin, and naphtho-1,2,3-triphosphorin. P
Valence Stabilizer #9a: Examples of 5-membered heterocyclic rings
containing one phosphorus atom and having at least one additional
phosphorus atom binding site not contained in a ring (P
Monodentates, P--P Bidentates, P--P Tridentates, P--P
Tetradentates, or P--P Hexadentates) that meet the requirements for
use as "narrow band" valence stabilizers for Co.sup.+3 include, but
are not limited to: 2-(P-phenylphosphino)-1-phospholene;
2,5-(P-phenylphosphino)-1-phospholene;
2-(P-phenylphosphino)-3-phospholene;
2,5-(P-phenylphosphino)-3-phospholene;
2-(P-phenylphosphino)phosphole; 2,5-(P-phenylphosphino)phosphole;
2-(P-phenylphosphino)benzophosphole;
7-(P-phenylphosphino)benzophosphole; and
1,8-(P-phenylphosphino)dibenzophosphole. P Valence Stabilizer #9b:
Examples of 5-membered heterocyclic rings containing two phosphorus
atoms and having at least one additional phosphorus atom binding
site not contained in a ring (P Monodentates, P--P Bidentates, P--P
Tridentates, P--P Tetradentates, or P--P Hexadentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to:
2-(P-phenylphospbino)-1,3-diphospholene;
2,5-(P-phenylphosphino)-1,3-diphospholene;
2-(P-phenylphosphino)-1,3-diphosphole;
2,5-(P-phenylphosphino)-1,3-diphosphole;
2-(P-phenylphosphino)benzodiphosphole; and
7-(P-phenylphosphino)benzodiphosphole. P Valence Stabilizer #9c:
Examples of 5-membered heterocyclic rings containing three
phosphorus atoms and having at least one additional phosphorus atom
binding site not contained in a ring (P Monodentates, P--P
Bidentates, P--P Tridentates, P--P Tetradentates, or P--P
Hexadentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
2-(P-phenylphosphino)-1,3,4-triphosphole; and
2,5-(P-phenylphosphino)-1,3,4-triphosphole. P Valence Stabilizer
#10a: Examples of 6-membered heterocyclic rings containing one
phosphorus atom and having at least one additional phosphorus atom
binding site not contained in a ring (P Monodentates, P--P
Bidentates, P--P Tridentates, P--P Tetradentates, or P--P
Hexadentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
2-(P-phenylphosphino)phosphorin; 2,5-(P-phenylphosphino)phosphorin;
2-(P-phenylphosphino)benzophosphorin;
7-(P-phenylphosphino)benzophosphorin; and
1,9-(P-phenylphosphino)acridophosphine. P Valence Stabilizer #10b:
Examples of 6-membered heterocyclic rings containing two phosphorus
atoms and having at least one additional phosphorus atom binding
site not
contained in a ring (P Monodentates, P--P Bidentates, P--P Trident
ates, P--P Tetradentates, or P--P Hexadentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to:
2-(P-phenylphosphino)-4-diphosphorin;
2,6-(P-phenylphosphino)-4-diphosphorin;
2,3,5,6-(P-phenylphosphino)-4-diphosphorin;
2-(P-phenylphosphino)benzo-1,4-diphosphorin;
2,3-(P-phenylphosphino)benzo-1,4-diphosphorin;
2,8-(P-phenylphosphino)benzo-1,4-diphosphorin;
2,3,5,8-(P-phenylphosphino)benzo-1,4-diphosphorin;
1,9-(P-phenylphosphino)dibenzodiphosphorin; and
1,4,6,9-(P-phenylphosphino)dibenzodiphosphorin. P Valence
Stabilizer #10c: Examples of 6-membered heterocyclic rings
containing three phosphorus atoms and having at least one
additional phosphorus atom binding site not contained in a ring (P
Monodentates, P--P Bidentates, P--P Tridentates, P--P
Tetradentates, or P--P Hexadentates) that meet the requirements for
use as "narrow band" valence stabilizers for Co.sup.+3 include, but
are not limited to: 2-(P-phenylphosphino)-1,3,5-triphosphorin;
2,6-(P-phenylphosphino)-1,3,5-triphosphorin;
4-(P-phenylphosphino)-1,2,3-triphosphorin; and
8-(P-phenylphosphino)benzo-1,2,3-triphosphorin. P Valence
Stabilizer#11a: Examples of 5-membered heterocyclic rings
containing one phosphorus atom and having at least one additional
phosphorus atom binding site contained in a ring (P Monodentates,
P--P Bidentates, P--P Tridentates, P--P Tetradentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: 2,2'-bi-1-phospholene;
2,2',2''-tri-1-phospholene; 2,2'-bi-3-phospholene; 2,2',
2''-tri-3-phospholene; 2,2'-biphosphole; 2,2',2''-triphosphole; and
2,2'-bibenzophosphole. P Valence Stabilizer#11b: Examples of
5-memberedheterocyclicrings containingtwo phosphorus atoms and
having at least one additional phosphorus atom binding site
contained in a ring (P Monodentates, P--P Bidentates, P--P
Tridentates, P--P Tetradentates) that meet the requirements for use
as "narrow band" valence stabilizers for Co.sup.+3 include, but are
not limited to: 2,2'-bi-1,3-diphospholene; 2,2'-bi-1,3-diphosphole;
and 2,2'-bibenzo-1,3-diphosphole. P Valence Stabilizer #11c:
Examples of 5-membered heterocyclic rings containing three
phosphorus atoms and having at least one additional phosphorus atom
binding site contained in a ring (P Monodentates, P--P Bidentates,
P--P Tridentates, P--P Tetradentates) that meet the requirements
for use as "narrow band" valence stabilizers for Co.sup.+3 include,
but are not limited to:2,2'-bi-1,3,4-triphosphole; and
2,2',2''-tri-1,3,4-triphosphole. P Valence Stabilizer #12a:
Examples of 6-membered heterocyclic rings containing one phosphorus
atom and having at least one additional phosphorus atom binding
site contained in a ring (P Monodentates, P--P Bidentates, P--P
Tridentates, P--P Tetradentates) that meet the requirements for use
as "narrow band" valence stabilizers for Co.sup.+3 include, but are
not limited to: 2,2'-biphosphorin; 2,2',2''-triphosphorin;
2,2',2'',2'''-tetraphosphorin; 2,2'-bibenzophosphorin; and
8,8'-bibenzophosphorin. P Valence Stabilizer #12b: Examples of
6-membered heterocyclic rings containing two phosphorus atoms and
having at least one additional phosphorus atom binding site
contained in a ring (P Monodentates, P--P Bidentates, P--P
Tridentates, P--P Tetradentates) that meet the requirements for use
as "narrow band" valence stabilizers for Co.sup.+3 include, but are
not limited to: 3,3'-bi-1,2-diphosphorin;
3,3',3''-tri-1,2-diphosphorin; 2,2'-bi-1,4-diphosphorin;
2,2',2''-tri-1,4-diphosphorin; 3,3'-bibenzo-1,2-diphosphorin;
8,8'-bibenzo-1,2-diphosphorin; 2,2'-bibenzo-1,4-diphosphorin; and
8,8'-bibenzo-1,4-diphosphorin. P Valence Stabilizer #12c: Examples
of 6-membered heterocyclic rings containing three phosphorus atoms
and having at least one additional phosphorus atom binding site
contained in a ring (P Monodentates, P--P Bidentates, P--P
Tridentates, P--P Tetradentates) that meet the requirements for use
as "narrow band" valence stabilizers for Co.sup.+3 include, but are
not limited to: 2,2'-bi-1,3,5-triphosphorin;
2,2',2''-tri-1,3,5-triphosphorin; 4,4'-bi-1,2,3-triphosphorin;
4,4'-bibenzo-1,2,3-triphosphorin; and
8,8'-bibenzo-1,2,3-triphosphorin. P Valence Stabilizer #13a:
Examples of two-membered macrocyclics, macrobicyclics, and
macropolycyclics (including catapinands, cryptands, cyclidenes, and
sepulchrates) wherein both binding sites are composed of phosphorus
and are not contained in component heterocyclic rings (P--P
Bidentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
P,P-diphenyldiphosphacyclobutane ([4]aneP.sub.2);
P,P-diphenyldiphosphacyclopentane ([5]aneP.sub.2);
P,P-diphenyldiphosphacyclohexane ([6]aneP.sub.2);
P,P-diphenyldiphosphacycloheptane ([7]aneP.sub.2);
P,P-diphenyldiphosphacyclooctane ([8]aneP.sub.2);
P,P-diphenyldiphosphacyclobutene ([4]eneP.sub.2);
P,P-diphenyldiphosphacyclopentene ([5]eneP.sub.2);
P,P-diphenyldiphosphacyclohexene ([6]eneP.sub.2);
P,P-diphenyldiphosphacycloheptene ([7]eneP.sub.2); and
P,P-diphenyldiphosphacyclooctene ([8]eneP.sub.2). P Valence
Stabilizer #13b: Examples of three-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all binding sites
are composed of phosphorus and are not contained in component
heterocyclic rings (P--P Tridentates) that meet the requirements
for use as "narrow band" valence stabilizers for Co.sup.+3 include,
but are not limited to: P,P,P-triphenyltriphosphacyclohexane
([6]aneP.sub.3); P,P,P-triphenyltriphosphacycloheptane
([7]aneP.sub.3); P,P,P-triphenyltriphosphacyclooctane
([8]aneP.sub.3); P,P,P-triphenyltriphosphacyclononane
([9]aneP.sub.3); P,P,P-triphenyltriphosphacyclodecane
([10]aneP.sub.3); P,P,P-triphenyltriphosphacycloundecane
([11]aneP.sub.3); P,P,P-triphenyltriphosphacyclododecane
([12]aneP.sub.3); P,P,P-triphenyltriphosphacyclohexatriene
([6]trieneP.sub.3); P,P,P-triphenyltriphosphacycloheptatriene
([7]trieneP.sub.3); P,P,P-triphenyltriphosphacyclooctatriene
([8]trieneP.sub.3); P,P,P-triphenyltriphosphacyclononatriene
([9]trieneP.sub.3); P,P,P-triphenyltriphosphacyclodecatriene
([10]trieneP.sub.3); P,P,P-triphenyltriphosphacycloundecatriene
([11]trieneP.sub.3); and P,P,P-triphenyltriphosphacyclododecatriene
([12]trieneP.sub.3). P Valence Stabilizer #13c: Examples of
four-membered macrocyclics, macrobicyclics, and macropolycyclics
(including catapinands, cryptands, cyclidenes, and sepulchrates)
wherein all binding sites are composed of phosphorus and are not
contained in component heterocyclic rings (P--P Tetradentates) that
meet the requirements foruse as "narrow band" valence stabilizers
for Co.sup.+3 include, but are not limited to:
P,P,P,P-tetraphenyltetraphosphacyclooctane ([8]aneP.sub.4);
P,P,P,P-tetraphenyltetraphosphacyclononane ([9]aneP.sub.4);
P,P,P,P-tetrapbenyltetraphosphacyclodecane ([10]aneP.sub.4);
P,P,P,P-tetraphenyltetraphosphacycloundecane ([11]aneP.sub.4);
P,P,P,P-tetraphenyltetraphosphacyclododecane ([12]aneP.sub.4);
P,P,P,P-tetraphenyltetrapbosphacyclotridecane ([13]aneP.sub.4);
P,P,P,P-tetraphenyltetraphosphacyclotetradecane ([14]aneP.sub.4);
P,P,P,P-tetraphenyltetraphosphacyclopentadecane ([15]aneP.sub.4);
P,P,P,P-tetraphenyltetraphosphacyclohexadecane ([16]aneP.sub.4);
P,P,P,P-tetraphenyltetraphosphacycloheptadecane ([17]aneP.sub.4);
P,P,P,P-tetraphenyltetraphosphacyclooctadecane ([18]aneP.sub.4);
P,P,P,P-tetraphenyltetraphosphacyclononadecane ([19]aneP.sub.4);
and P,P,P,P-tetraphenyltetraphosphacycloeicosane ([20]aneP.sub.4).
P Valence Stabilizer #13d: Examples of five-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all binding sites
are composed of phosphorus and are not contained in component
heterocyclic rings (P--P Tridentates, or P--P Tetradentates) that
meet the requirements for use as "narrow band" valence stabilizers
for Co.sup.+3 include, but are not limited to:
P,P,P,P,P-pentaphenylpentaphosphacyclodecane ([10]aneP.sub.5);
P,P,P,P,P-pentaphenylpentaphosphacycloundecane ([11]aneP.sub.5);
P,P,P,P,P-pentaphenylpentaphosphacyclododecane ([12]aneP.sub.5);
P,P,P,P,P-pentaphenylpentaphosphacyclotridecane ([13]aneP.sub.5);
P,P,P,P,P-pentaphenylpentaphosphacyclotetradecane ([14]aneP.sub.5);
and P,P,P,P,P-pentaphenylpentaphosphacyclopentadecane
([15]aneP.sub.5). P Valence Stabilizer #13e: Examples of
six-membered macrocyclics, macrobicyclics, and macropolycyclics
(including catapinands, cryptands, cyclidenes, and sepulchrates)
wherein all binding sites are composed of phosphorus and are not
contained in component heterocyclic rings (P--P--P Tridentates,
P--P--P--P Tetradentates, or P--P--P--P--P--P Hexadentates) that
meet the requirements for use as "narrow band" valence stabilizers
for Co.sup.+3 include, but are not limited to:
P,P,P,P,P,P-hexaphenylhexaphosphacyclododecane ([12]aneP.sub.6);
P,P,P,P,P,P-hexaphenylhexaphosphacyclotridecane ([13]aneP.sub.6);
P,P,P,P,P,P-hexaphenylhexaphosphacyclotetradecane ([14]aneP.sub.6);
P,P,P,P,P,P-hexaphenylhexaphosphacyclopentadecane ([15]aneP.sub.6);
P,P,P,P,P,P-hexaphenylhexaphosphacyclohexadecane ([16]aneP.sub.6);
P,P,P,P,P,P-hexaphenylhexaphosphacycloheptadecane ([17]aneP.sub.6);
P,P,P,P,P,P-hexaphenylhexaphosphacyclooctadecane ([18]aneP.sub.6);
P,P,P,P,P,P-hexaphenylhexaphosphacyclononadecane ([19]aneP.sub.6);
P,P,P,P,P,P-hexaphenylhexaphosphacycloeicosane ([20]aneP.sub.6);
P,P,P,P,P,P-hexaphenylhexaphosphacycloheneicosane ([21]aneP.sub.6);
P,P,P,P,P,P-hexaphenylhexaphosphacyclodocosane ([22]aneP.sub.6);
P,P,P,P,P,P-hexaphenylhexaphosphacyclotricosane ([23]aneP.sub.6);
P,P,P,P,P,P-hexaphenylhexaphosphacyclotetracosane ([24]aneP.sub.6).
P Valence Stabilizer #13f: Examples of eight-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all binding sites
are composed of phosphorus and are not contained in component
heterocyclic rings (P--P Tridentates, P--P Tetradentates, or P--P
Hexadentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
P,P,P,P,P,P,P,P-octaphenyloctaphosphacyclohexadecane
([16]aneP.sub.8);
P,P,P,P,P,P,P,P-octaphenyloctaphosphacycloheptadecane
([17]aneP.sub.8);
P,P,P,P,P,P,P,P-octaphenyloctaphosphacyclooctadecane
([18]aneP.sub.8);
P,P,P,P,P,P,P,P-octaphenyloctaphosphacyclononadecane
([19]aneP.sub.8);
P,P,P,P,P,P,P,P-octaphenyloctaphosphacycloeicosane
([20]aneP.sub.8);
P,P,P,P,P,P,P,P-octaphenyloctaphosphacycloheneicosane
([21]aneP.sub.8);
P,P,P,P,P,P,P,P-octaphenyloctaphosphacyclodocosane
([22]aneP.sub.8);
P,P,P,P,P,P,P,P-octaphenyloctaphosphacyclotricosane
([23]aneP.sub.8); and
P,P,P,P,P,P,P,P-octaphenyloctaphosphacyclotetracosane
([24]aneP.sub.8). P Valence Stabilizer #14a: Examples of
four-membered macrocyclics, macrobicyclics, and macropolycyclics
(including catapinands, cryptands, cyclidenes, and sepulchrates)
wherein all four binding sites are composed of phosphorus and are
contained in component 5-membered heterocyclic rings (P--P
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
tetraphospholenes; tetraphospholes; tetraoxaphospholes;
tetradiphospholenes; tetradiphospholes; and tetraoxadiphospholes. P
Valence Stabilizer #14b: Examples of six-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all six binding
sites are composed of phosphorus and are contained in component
5-membered heterocyclic rings (P--P Tetradentates and P--P
Hexadentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
hexaphospholenes; hexaphospholes; hexaoxaphospholes;
hexadiphospholenes; hexadiphospholes; and hexaoxadiphospholes. P
Valence Stabilizer #14c: Examples of eight-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all eight binding
sites are composed of phosphorus and are contained in component
5-membered heterocyclic rings (P--P Tridentates; P--P
Tetradentates; or P--P Hexadentates) that meet the requirements for
use as "narrow band" valence stabilizers for Co.sup.+3 include, but
are not limited to: octaphospholenes; octaphospholes;
octaoxaphospholes; octadiphospholenes; octadiphospholes; and
octaoxadiphospholes. P Valence Stabilizer #15a: Examples of
four-membered macrocyclics, macrobicyclics, and macropolycyclics
(including catapinands, cryptands, cyclidenes, and sepulchrates)
wherein all four binding sites are composed of phosphorus and are
contained in a combination of 5-membered heterocyclic rings and
phosphine groups (P--P Tridentates, P--P Tetradentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to:
diphosphatetraphospholenes; tetraphosphatetraphospholenes;
diphosphatetraphospholes; tetraphosphatetraphospboles;
diphoshatetradiphospholes; and tetraphosphatetradiphospholes. P
Valence Stabilizer #15b: Examples of six-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all six binding
sites are composed of phosphorus and are contained in a combination
of 5-membered heterocyclic rings and phosphine groups (P--P
Tridentates, P--P Tetradentates, and P--P Hexadentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to:
diphosphahexaphospholenes; triaphosphahexaphospholenes;
diphosphahexaphospholes; triphosphahexaphospholes;
diphoshahexadiphospholes; and triphosphahexadiphospholes. P Valence
Stabilizer #15c: Examples of eight-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all eight binding
sites are composed of phosphorus and are contained in a combination
of 5-membered heterocyclic rings and phosphine groups (P--P
Tridentates, P--P Tetradentates, and P--P Hexadentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to:
diphosphaoctaphospholenes; tetraphosphaoctaphospholenes;
diphosphaoctaphospholes; tetraphosphaoctaphospholes;
diphoshaoctadiphospholes; and tetraphosphaoctadiphospholes. P
Valence Stabilizer #16a: Examples of four-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all four binding
sites are composed of phosphorus and are contained in component
6-membered heterocyclic rings (P--P Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: cyclotetraphosphorins;
cyclotetraaoxaphosphorins; cyclotetradiphosphorins; and
cyclotetraoxadiphosphorins. P Valence Stabilizer #16b: Examples of
six-membered macrocyclics, macrobicyclics, and macropolycyclics
(including catapinands, cryptands, cyclidenes, and sepulchrates)
wherein all six binding sites are composed of phosphorus and are
contained in component 6-membered heterocyclic rings (P--P
Tridentates, P--P Tetradentates, and P--P Hexadentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: cyclohexaphosphorins;
cyclohexaoxaphosphorins; cyclohexadiphosphorins; and
cyclohexaoxadiphosphorins. P Valence Stabilizer #16c: Examples of
eight-membered macrocyclics, macrobicyclics, and macropolycyclics
(including catapinands, cryptands, cyclidenes, and sepulchrates)
wherein all eight binding sites are composed of phosphorus and are
contained in component 6-membered heterocyclic rings (P--P
Tridentates, P--P Tetradentates, and P--P Hexadentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: cyclooctaphosphorins;
cyclooctaoxaphosphorins; cyclooctadiphosphorins; and
cyclooctaoxadiphosphorins. P Valence Stabilizer #17a: Examples of
four-membered macrocyclics, macrobicyclics, and
macropolycyclics
(including catapinands, cryptands, cyclidenes, and sepulchrates)
wherein all four binding sites are composed of phosphorus and are
contained in a combination of 6-membered hetero cyclic rings and
phosphine groups (P--P Tridentates, P--P Tetradentates, or P--P
Hexadentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
diphosphacyclotetraphosphorins; tetraphosphacyclotetraphosphorins;
diphosphacyclotetraoxaphosphorins;
tetraphosphacyclotetraoxaphosphorins;
diphosphacyclotetradiphosphorins;
tetraphosphacyclotetradiphosphorins;
diphosphacyclotetraoxadiphosphorins; and
tetraphosphacyclotetraoxadiphosphorins. P Valence Stabilizer #17b:
Examples of six-membered macrocyclics, macrobicyclics, and
macropolycyclics (including catapinands, cryptands, cyclidenes, and
sepulchrates) wherein all six binding sites are composed of
phosphorus and are contained in a combination of 6-membered
heterocyclic rings and phosphine groups (P--P Tridentates, P--P
Tetradentates, or P--P Hex adentates) that meet the requirements
for use as "narrow band" valence stabilizers for Co.sup.+3 include,
but are not limited to: diphosphacyclohexaphosphorins;
triphosphacyclohexaphosphorins; diphosphacyclohexaoxaphosphorins;
triphosphacyclohexaoxaphosphorins; diphosphacyclohexadiphosphorins;
triphosphacyclohexadiphosphorins;
diphosphacyclohexaoxadiphosphorins; and
triphosphacyclohexaoxadiphosphorins. P Valence Stabilizer #17c:
Examples of eight-membered macrocyclics, macrobicyclics, and
macropolycyclics (including catapinands, cryptands, cyclidenes, and
sepulchrates) wherein all eight binding sites are composed of
phosphorus and are contained in a combination of 6-membered
heterocyclic rings and phosphine groups (P--P Tridentates, P--P
Tetradentates, or P--P Hexadentates) that meet the requirements for
use as "narrow band" valence stabilizers for Co.sup.+3 include, but
are not limited to: diphosphacyclooctaphosphorins;
tetraphosphacyclooctaphosphorins; diphosphacyclooctaoxaphosphorins;
tetraphosphacyclooctaoxaphosphorins;
diphosphacyclooctadiphosphorins;
tetraphosphacyclooctadiphosphorins;
diphosphacyclooctaoxadiphosphorins; and
tetraphosphacyclooctaoxadiphosphorins. O Valence Stabilizer #1:
Examples of biurets (imidodicarbonic diamides), isobiurets,
biureas, triurets, triureas, bis(biurets), bis(isobiurets),
bis(biureas), poly(biurets), poly(isobiurets), and poly(biureas)
(O--O Bidentates, O--O Tridentates, O--O Tetradentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: biuret, isobiuret,
biurea, triuret, triurea, nitrobiuret, dinitrobiuret, aminobiuret,
diaminobiuret, oxybiuret, dioxybiuret, cyanobiuret, methylbiuret,
ethylbiuret, isopropylbiuret, phenylbiuret, benzylbiuret,
cyclohexylbiuret, norbornylbiuret, adamantylbiuret, dimethylbiuret,
diethylbiuret, diisopropylbiuret, diphenylbiuret, dibenzylbiuret,
dicyclohexylbiuret, dinorbornylbiuret, and diadamantylbiuret. O
Valence Stabilizer #2: Examples of acylureas, aroylureas,
bis(acylureas), bis(aroylureas), poly(acylureas), and
poly(aroylureas) (O--O Bidentates, O--O Tridentates, O--O
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
formylurea, acetylurea, benzoylurea, cyclohexoylurea,
pentafluorobenzoylurea, N-methylacetylurea, N-phenylbenzoylurea,
and N-cyclohexylcyclohexoylurea. O Valence Stabilizer #3: Examples
of imidodialdehydes, hydrazidodialdehydes (acyl hydrazides),
bis(imidodialdehydes), bis(hydrazidodialdehydes),
poly(imidodialdehydes), and poly(hydrazidodialdehydes) (O--O
Bidentates, O--O Tridentates, O--O Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: diacetamide,
dipropanamide, dibutanamide, dibenzamide, and dicyclohexamide. O
Valence Stabilizer #4: Examples of imidodicarbonic acids,
hydrazidodicarbonic acids, bis(imidodicarbonic acids),
bis(hydrazidodicarbonic acids), poly(imidodicarbonic acids),
poly(hydrazidodicarbonic acids) and derivatives thereof (O--O
Bidentates, O--O Tridentates, O--O Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: imidodicarbonic acid,
hydrazidodicarbonic acid, O-phenylimidodicarbonic acid,
O-benzylimidodicarbonic acid, O-cyclohexylimidodicarbonic acid,
O-norbornylimidodicarbonic acid, O,O'-diphenylimidodicarbonic acid,
O,O'-dibenzylimidodicarbonic acid, O,O'-dicyclohexylimidodicarbonic
acid, and O,O'-dinorbornylimidodicarbonic acid. O Valence
Stabilizer #5: Examples of imidodisulfamic acid, imidodisulfuric
acid, bis(imidodisulfamic acid), bis(imidodisulfuric acid),
poly(imidodisulfamic acid), and poly(imidodisulfuric acid) and
derivatives thereof (O--O Bidentates, O--O Tridentates, O--O
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
imidodisulfamic acid, imidodisulfuric acid, N-phenylimidodisulfamic
acid, N-benzylimidodisulfamic acid, N-cyclohexylimidodisulfamic
acid, N-norbornylimidodisulfamic acid, N,N'-diphenylimidodisulfamic
acid, N,N'-dibenzylimidodisulfamic acid,
N,N'-dicyclohexylimidodisulfamic acid, and
N,N'-norbornylimidodisulfamic acid. O Valence Stabilizer #6:
Examples of 1,3-diketones (beta-diketonates), 1,3,5-triketones,
bis(1,3-diketones), and poly(1,3-diketones), all with a molecular
weight greater than 125 (O--O Bidentates, O--O Tridentates, O--O
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
hexafluoropentanedione; dibenzoylmethane
(1,3-diphenyl-1,3-propanedione); benzoylpinacolone;
dicyclohexoylmethane; diphenylpentanetrionate; dibenzoylacetone;
benzoylacetylacetone; dibenzoylacetylacetone;
tetramethylnonanetrionate; hexafluoroheptanetrionate;
trifluoroheptanetrionate; trifluoroacetylcamphor (facam); and
1,3-indandione. O Valence Stabilizer #7: Examples of 1,2-diketones
(alpha-diketonates), 1,2,3-triketones, tropolonates, o-quinones,
bis(1,2-diketones), and poly(1,2-diketones), all with a molecular
weight greater than 100 (O--O Bidentates, O--O Tridentates, O--O
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
tropolone; 1,2-benzoquinone (o-quinone);
di-tert-butyl-1,2-benzoquinone; hexafluoro-1,2-benzoquinone;
1,2-naphthoquinone; 9,10-phenanthroquinone; and 1,2-indandione. O
Valence Stabilizer #8: Examples of malonamides (malonodiamides),
bis(malonamides), and polymalonamides (O--O Bidentates, O--O
Tridentates, O--O Tetradentates) that meet the requirements for use
as "narrow band" valence stabilizers for Co.sup.+3 include, but are
not limited to: malonamide, N-phenylmalonamide, N-benzylmalonamide,
N-pentafluorophenylmalonamide, N-cyclohexylmalonamide,
N-norbornylmalonamide, N,N'-diphenylmalonamide,
N,N'-dibenzylmalonamide, N,N'-dipentafluorophenylmalonamide,
N,N'-dicyclohexylmalonamide, and N,N'-norbornylmalonamide. O
Valence Stabilizer #9: Examples of 2-acylacetamides,
bis(2-acylacetamides), and poly(2-acylacetamides) (O--O Bidentates,
O--O Tridentates, O--O Tetradentates) that meet the requirements
for use as "narrow band" valence stabilizers for Co.sup.+3 include,
but are not limited to: 2-acetoacetamide,
N-phenyl-2-acetoacetamide, N-pentafluorophenyl-2-acetoacetamide,
N-benzyl-2-acetoacetamide, N-cyclohexyl-2-acetoacetamide,
N-norbornyl-2-acetoacetamide, N-phenyl-2-benzoacetamide,
N-pentafluorophenyl-2-pentafluorobenzoacetamide, and
N-cyclohexyl-2-cyclohexoacetamide. O Valence Stabilizer #10:
Examples of monothiodicarbonic diamides, bis(monothiodicarbonic
diamides), and poly(monothiodicarbonic diamides) (O--O Bidentates,
O--O Tridentates, O--O Tetradentates) that meet the requirements
for use as "narrow band" valence stabilizers for Co.sup.+3 include,
but are not limited to: monothiodicarbonic diamide;
N-phenylmonothiodicarbonic diamide;
N-pentafluorophenylmonothiodicarbonic diamide;
N-benzylmonothiodicarbonic diamide; N-cyclohexylmonothiodicarbonic
diamide; N-norbornylmonothiodicarbonic diamide;
N,N'-diphenylmonothiodicarbonic diamide;
N,N'-dipentafluorophenylmonothiodicarbonic diamide;
N,N'-dibenzylmonothiodicarbonic diamide;
N,N'-dicyclohexylmonothiodicarbonic diamide; and
N,N'-dinorbornylmonothiodicarbonic diamide. O Valence Stabilizer
#11: Examples ofmonothiodicarbonic acids, bis(monothiodicarbonic
acids), poly(monothiodicarbonic acids), and derivatives thereof
(O--O Bidentates, O--O Tridentates, O--O Tetradentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: monothiodicarbonic acid,
O-phenylmonothiodicarbonic acid, O-benzylmonothiodicarbonic acid,
O-cyclohexylmonothiodicarbonic acid, O-norbornylmonothiodicarbonic
acid, O,O'-diphenylmonothiodicarbonic acid,
O,O'-dibenzylmonothiodicarbonic acid,
O,O'-dicyclohexylmonothiodicarbonic acid, and
O,O'-dinorbornylmonothiodicarbonic acid. O Valence Stabilizer #12:
Examples of dithioperoxydicarbonic acids,
bis(dithioperoxydicarbonic acids), poly(dithioperoxydicarbonic
acids), and derivatives thereof (O--O Bidentates, O--O Tridentates,
O--O Tetradentates) that meet the requirements for use as "narrow
band" valence stabilizers for Co.sup.+3 include, but are not
limited to: dithioperoxydicarbonic acid,
O-phenyldithioperoxydicarbonic acid; O-benzyldithioperoxydicarbonic
acid; O-cyclohexyldithioperoxydicarbonic acid;
O-norbornyldithioperoxydicarbonic acid;
O,O'-diphenyldithioperoxydicarbonic acid;
O,O'-dibenzyldithioperoxydicarbonic acid;
O,O'-dicyclohexyldithioperoxydicarbonic acid; and
O,O'-dinorbornyldithioperoxydicarbonic acid. O Valence Stabilizer
#13: Examples oftrithionic acid, bis(trithionic acid),
poly(trithionic acid), and derivatives thereof (O--O Bidentates,
O--O Tridentates, O--O Tetradentates) that meet the requirements
for use as "narrow band" valence stabilizers for Co.sup.+3 include,
but are not limited to: diphenyl trithionate, dipentafluorodiphenyl
trithionate, dicyclohexyl trithionate, and dinorbornyl trithionate.
O Valence Stabilizer #14: Examples of hypophosphoric acids,
bis(hypophosphoric acids), and poly(hypophosphoric acids), and
derivatives thereof (O--O Bidentates, O--O Tridentates, O--O
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
hypophosphoric acid, O-methylhypophosphoric acid,
O-isopropylhypophosphoric acid, O-tert-butylhypophosphoric acid,
O-phenylhypophosphoric acid, O-pentafluorophenylhypophosphoric
acid, O-benzylhypophosphoric acid, O-cyclohexylhypophosphoric acid,
O-norbornylhypophosphoric acid, O,O''-dimethylhypophosphoric acid,
O,O''-diisopropylhypophosphoric acid,
O,O''-di-tert-butylhypophosphoric acid,
O,O''-diphenylhypophosphoric acid,
O,O''-di-pentafluorophenylhypophosphoric acid,
O,O''-dibenzylhypophosphoric acid, O,O''-dicyclohexylhypophosphoric
acid, and O,O''-dinorbornylhypophosphoric acid. O Valence
Stabilizer #15: Examples of hypophosphoramides,
bis(hypophosphoramides), and poly(hypophosphoramides) (O--O
Bidentates, O--O Tridentates, O--O Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: hypophosphoramide,
N-methylhypophosphoramide, N-isopropylhypophosphoramide,
N-tert-butylhypophosphoramide, N-phenylhypophosphoramide,
N-pentafluorophenylhypophosphoramide, N-benzylhypophosphoramide,
N-cyclohexylhypophosphoramide, N-norbornylhypophosphoramide,
N,N'''-dimethylhypophosphoramide,
N,N'''-diisopropylhypophosphoramide,
N,N'''-di-tert-butylhypophosphoramide,
N,N'''-diphenylhypophosphoramide,
N,N'''-di-pentafluorophenylhypophosphoramide,
N,N'''-dibenzylhypophosphoramide,
N,N'''-dicyclohexylhypophosphoramide, and
N,N'''-dinorbornylhypophosphoramide. O Valence Stabilizer #16:
Examples of imidodiphosphoric acids, hydrazidodiphosphoric acids,
bis(imidodiphosphoric acids), bis(hydrazidodiphosphoric acids),
poly(imidodiphosphoric acids), poly(hydrazidodiphosphoric acids),
and derivatives thereof(O--O Bidentates, O--O Tridentates, O--O
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
imidodiphosphoric acid, methylimidodiphosphoric acid,
isopropylimidodiphosphoric acid, tert-butylimidodiphosphoric acid,
phenylimidodiphosphoric acid, pentafluorophenylimidodiphosphoric
acid, benzylimidodiphosphoric acid, cyclohexylimidodiphosphoric
acid, norbornylimidodiphosphoric acid, dimethylimidodiphosphoric
acid, diisopropylimidodiphosphoric acid,
di-tert-butylimidodiphosphoric acid, diphenylimidodiphosphoric
acid, di-pentafluorophenylimidodiphosphoric acid,
dibenzylimidodiphosphoric acid, dicyclohexylimidodiphosphoric acid,
and dinorbornylimidodiphosphoric acid. O Valence Stabilizer #17:
Examples of imidodiphosphoramides, hydrazidodiphosphoramides,
bis(imidodiphosphoramides), bis(hydrazidodiphosphoramides),
poly(imidodiphosphoramides), and poly(hydrazidodiphosphoramides)
(O--O Bidentates, O--O Tridentates, O--O Tetradentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: imidodiphosphoramide,
N-methylimidodiphosphoramide, N-isopropylimidodiphosphoramide,
N-tert-butylimidodiphosphoramide, N-phenylimidodiphosphoramide,
N-pentafluorophenylimidodiphosphoramide,
N-benzylimidodiphosphoramide, N-cyclohexylimidodiphosphoramide,
N-norbornylimidodiphosphoramide,
N,N'''-dimethylimidodiphosphoramide,
N,N'''-diisopropylimidodiphosphoramide,
N,N'''-di-tert-butylimidodiphosphoramide,
N,N'''-diphenylimidodiphosphoramide,
N,N'''-di-pentafluorophenylimidodiphosphoramide,
N,N'''-dibenzylimidodiphosphoramide,
N,N'''-dicyclohexylimidodiphosphoramide, and
N,N'''-dinorbornylimidodiphosphoramide. O Valence Stabilizer #18:
Examples of diphosphoramides, bis(diphosphoramides), and
poly(diphospboramides) (O--O Bidentates, O--O Tridentates, O--O
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
diphosphoramide, N-methyldiphosphoramide,
N-isopropyldiphosphoramide, N-tert-butyldiphosphoramide,
N-phenyldiphosphoramide, N-pentafluorophenyldiphosphoramide,
N-benzyldiphosphoramide, N-cyclohexyldiphosphoramide,
N-norbornyldiphosphoramide, N,N'''-dimethyldiphosphoramide,
N,N'''-diisopropyldiphosphoramide,
N,N'''-di-tert-butyldiphosphoramide,
N,N'''-diphenyldiphosphoramide,
N,N'''-di-pentafluorophenyldiphosphoramide,
N,N'''-dibenzyldiphosphoramide, N,N'''-dicyclohexyldiphosphoramide,
and N,N'''-dinorbornyldiphosphoramide. O Valence Stabilizer #19:
Examples of imidodiphosphonic acids, hydrazidodiphosphonic acids,
bis(imidodiphospbonic acids), bis(hydrazidodiphospbonic acids),
poly(imidodiphosphonic acids), poly(hydrazidodiphosphonic acids),
and derivatives thereof (O--O Bidentates, O--O Tridentates, O--O
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
imidodiphosphonic acid, methylimidodiphosphonic acid,
isopropylimidodiphosphonic acid, tert-butylimidodiphosphonic acid,
phenylimidodiphosphonic acid, pentafluorophenylimidodiphosphonic
acid, benzylimidodiphosphonic acid, cyclohexylimidodiphosphonic
acid, norbornylimidodiphosphonic acid, dimethylimidodiphosphonic
acid, diisopropylimidodiphosphonic acid,
di-tert-butylimidodiphosphonic acid, diphenylimidodiphosphonic
acid, di-pentafluorophenylimidodiphosphonic acid,
dibenzylimidodiphosphonic acid, dicyclohexylimidodiphosphonic acid,
and dinorbornylimidodiphosphonic acid. [Note: The phosphite
(P.sup.+3) valence of the phosphorus atom makes stabilizization of
high valence metal ions much more difficult, though still
possible.] O Valence Stabilizer #20: Examples of
imidodiphosphonamides, hydrazidodiphosphonamides,
bis(imidodiphosphonamides), bis(hydrazidodiphosphonamides),
poly(imidodiphosphonamides), and poly(hydrazidodiphosphonamides)
(O--O Bidentates, O--O Tridentates, O--O Tetradentates) that meet
the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
imidodiphosphonamide, N-methylimidodiphosphonamide,
N-isopropylimidodiphosphonamide, N-tert-butylimidodiphosphonamide,
N-phenylimidodiphosphonamide,
N-pentafluorophenylimidodiphosphonamide,
N-benzylimidodiphosphonamide, N-cyclohexylimidodiphosphonamide,
N-norbornylimidodiphosphonamide,
N,N'''-dimethylimidodiphosphonamide,
N,N'''-diisopropylimidodiphosphonamide,
N,N'''-di-tert-butylimidodiphosphonamide,
N,N'''-diphenylimidodiphosphonamide,
N,N'''-di-pentafluorophenylimidodiphosphonamide,
N,N'''-dibenzylimidodiphosphonamide,
N,N'''-dicyclohexylimidodiphosphonamide, and
N,N'''-dinorbornylimidodiphosphonamide. [Note: The phosphite
(P.sup.+3) valence of the phosphorus atom makes stabilizization of
high valence metal ions much more difficult, though still
possible.] O Valence Stabilizer #21: Examples of diphosphonamides,
bis(diphosphonamides), and poly(diphosphonamides) (O--O Bidentates,
O--O Tridentates, O--O Tetradentates) that meet the requirements
for use as "narrow band" valence stabilizers for Co.sup.+3 include,
but are not limited to: diphosphonamide, N-methyldiphosphonamide,
N-isopropyldiphosphonamide, N-tert-butyldiphosphonamide,
N-phenyldiphosphonamide, N-pentafluorophenyldiphosphonamide,
N-benzyldiphosphonamide, N-cyclohexyldiphosphonamide,
N-norbornyldiphosphonamide, N,N'''-dimethyldiphosphonamide,
N,N'''-diisopropyldiphosphonamide,
N,N'''-di-tert-butyldiphosphonamide,
N,N'''-diphenyldiphosphonamide,
N,N'''-di-pentafluorophenyldiphosphonamide,
N,N'''-dibenzyldiphosphonamide, N,N'''-dicyclohexyldiphosphonamide,
and N,N'''-dinorbornyldiphosphonamide. [Note: The phosphite
(P.sup.+3) valence of the phosphorus atom makes stabilizization of
high valence metal ions much more difficult, though still
possible.] O Valence Stabilizer #22: Examples of
beta-hydroxyketones, beta-hydroxyaldehydes,
bis(beta-hydroxyketones), bis(beta-hydroxyaldehydes),
poly(beta-hydroxyketones), and poly(beta-hydroxyaldehydes) (O--O
Bidentates, O--O Tridentates, O--O Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: 4-hydroxypentan-2-one;
1,3-diphenyl-3-hydroxypropanal; 1,3-dibenzyl-3-hydroxypropanal;
1,3-dicyclohexyl-3-hydroxypropanal;
1,3-dinorbornyl-3-hydroxypropanal;
1,3-di(2-thienyl)-3-hydroxypropanal;
1,3-di(2-furyl)-3-hydroxypropanal; o-hydroxyacetophenone; juglone;
alizarin; 1-hydroxyanthraquinone; 1,8-hydroxyanthraquinone;
1-hydroxyacridone; and beta-hydroxybenzophenone. O Valence
Stabilizer #23: Examples of N-(aminomethylol)ureas
[N-(aminohydroxymethyl)ureas], bis[N-(aminomethylol)ureas], and
poly[N-(aminomethylol)ureas] (O--O Bidentates, O--O Tridentates,
O--O Tetradentates) that meet the requirements for use as "narrow
band" valence stabilizers for Co.sup.+3 include, but are not
limited to: N'-(aminohydroxymethyl)urea;
N,N''-dimethyl-N'-(aminohydroxymethyl)urea;N,N'-diethyl-N'-(aminohydroxym-
ethyl)urea; N,N''-isopropyl-N'-(aminohydroxymethyl)urea;
N,N''-diphenyl-N'-(aminohydroxymethyl)urea;
N,N''-dibenzyl-N'-(aminohydroxymethyl)urea;
N,N''-dicyclohexyl-N'-(aminohydroxymethyl)urea; and
N,N''-dinorbornyl-N'-(aminohydroxymethyl)urea. O Valence Stabilizer
#24: Examples of oxamides, bis(oxamides), and poly(oxamides) (O--O
Bidentates, O--O Tridentates, O--O Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: oxamide,
N-methyloxamide; N-ethyloxamide; N-isopropyloxamide;
N-phenyloxamide; N-benzyloxamide; N-cyclohexyloxamide;
N-norbornyloxamide; N,N'-dimethyloxamide; N,N'-diethyloxamide;
N,N'-diisopropyloxamide; N,N'-diphenyloxamide;
N,N'-dibenzyloxamide; N,N'-dicyclohexyloxamide; and
N,N'-dinorbornyloxamide. O Valence Stabilizer #25: Examples of
squaric acids and derivatives thereof (O--O Bidentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: deltic acid; squaric
acid; croconic acid; and rhodizonic acid. O Valence Stabilizer #26:
Examples of dicarboxylic acids, bis(dicarboxylic acids),
poly(dicarboxylic acids), and derivatives thereof (O--O Bidentates
and O--O Tetradentates) that meet the requirements for use as
"narrow band" valence stabilizers for Co.sup.+3 include, but are
not limited to: oxalic acid; malonic acid; succinic acid; diphenyl
oxalate; diphenyl malonate; and diphenyl succinate. O Valence
Stabilizer #27: Examples of carbonates and bis(carbonates) (O--O
Bidentates and O--O Tetradentates) that meet the requirements for
use as "narrow band" valence stabilizers for Co.sup.+3 include, but
are not limited to: carbonate; bicarbonate; O,O-diethylcarbonate;
diisopropylcarbonate; diphenylcarbonate; dibenzylcarbonate;
dicyclohexylcarbonate; and dinorbornylcarbonate. O Valence
Stabilizer #28: Examples of carbamates, bis(carbamates), and
poly(carbamates) (including N-hydroxycarbamates and
N-mercaptocarbamates) (O--O Bidentates, O--O Tridentates, and O--O
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
dimethylcarbamate (dmc); di(trifluorodimethyl)carbamate; ethyl
carbamate; diethylcarbamate (dec); dipropylcarbamate;
diisopropylcarbamate; dibutylcarbamate; ditertbutylcarbamate;
dicyanamidocarbamate; diphenylcarbamate;
di(pentafluorophenyl)carbamate; dibenzylcarbamate;
dinaphthylcarbamate; dicyclohexylcarbamate; dinorbornylcarbamate;
diadamantylcarbamate; pyrrolidinocarbamate (pyrc);
piperidinocarbamate (pipc); morpholinocarbamate (more);
thiamorpholinocarbamate; 3-pyrrolinocarbamate; pyrrolocarbamate;
oxazolocarbamate; isoxazolocarbamate; thiazolocarbamate;
isothiazolocarbamate; indolocarbamate; carbazolocarbamate;
pyrazolinocarbamate; imidazolinocarbamate; pyrazolocarbamate;
imidazolocarbamate; indazolocarbamate; and triazolocarbamate. O
Valence Stabilizer #29: Examples of carbazates (carbazides),
bis(carbazates), and poly(carbazates) (O--O Bidentates, O--O
Tridentates, and O--O Tetradentates; or possibly N--O Bidentates,
N--O Tridentates, and N--O Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: N,N'-dimethylcarbazate;
N,N'-di(trifluoromethyl)carbazate; N,N'-diethylcarbazate;
N,N'-diphenylcarbazate; N,N'-dibenzylcarbazate;
N,N'-di(pentafluorophenyl)carbazate; N,N'-dicyclohexylcarbazate;
and N,N'-dinorbornylcarbazate. O Valence Stabilizer #30: Examples
of carbimates, bis(carbimates), and poly(carbimates) (O--O
Bidentates, O--O Tridentates, and O--O Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: methylcarbimate;
trifluoromethylcarbimate; etbylcarbimate; propylcarbimate;
isopropylcarbimate; butylcarbimate; tertbutylcarbimate;
cyanocarbimate; cyanamidocarbimate; azidocarbimate;
phenylcarbimate; pentafluorophenylcarbimate; benzylcarbimate;
naphthylcarbimate; cyclohexylcarbimate; norbornylcarbimate; and
adamantylcarbimate. [Note: Carbimates tend to stabilize lower
oxidation states in metal ions.] O Valence Stabilizer #31: Examples
of arsonic acids, bis(arsonic acids), poly(arsonic acids), and
derivatives thereof (O--O Bidentates, O--O Tridentates, O--O
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
arsonic acid, O-phenylarsonic acid, O-benzylarsonic acid,
O-cyclohexylarsonic acid, O-norbornylarsonic acid,
O,O-diphenylarsonic acid, O,O-dibenzylarsonic acid,
O,O-dicyclohexylarsonic acid, O,O-dinorbornylarsonic acid; and
aminophenylarsonic acids. O Valence Stabilizer #32: Examples of
alkyl- and aryl-borates and bis(borates) (O--O Bidentates and O--O
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
triethyl borate; diisopropyl borate; diphenyl borate; dibenzyl
borate; dicyclohexyl borate; and dinorbornyl borate. O Valence
Stabilizer #33: Examples of alkyl- and aryl-boronates and
bis(boronates) (O--O Bidentates and O--O Tetradentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: diethyl boronate;
diisopropyl boronate; diphenyl boronate; dibenzyl boronate;
dicyclohexyl boronate; and dinorbornyl boronate. [Note: boronates
tend to stabilize lower oxidation states in metal ions.] O Valence
Stabilizer #34: Examples of phosphine P-oxides and
amino-substituted phosphine oxides (O Monodentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: trimethylphosphine oxide
(TMPO); triethylphosphine oxide (TEPO); triphenylphosphine oxide
(TPhPO); tribenzylphosphine oxide (TBzPO); tricyclohexylphosphine
oxide (TcHxPO); and trinorbornylphosphine oxide for phosphine
P-oxides; and hexamethylphosphoramide (HMPA);
trimorpholinophosphine oxide (TMrPO); tripiperidinophosphine oxide;
tripyrrolidinophosphine oxide; and tri(cyclohexylamino)phosphine
oxide for amino-substituted phosphine oxides. O Valence Stabilizer
#35: Examples of arsine As-oxides and amino-substituted arsine
oxides (O Monodentates) that meet the requirements for use as
"narrow band" valence stabilizers for Co.sup.+3 include, but are
not limited to: trimethylarsine oxide (TMAsO); triethylarsine oxide
(TEAsO); triphenylarsine oxide (TPhAsO); tribenzylarsine oxide
(TBzAsO); tricyclohexylarsine oxide (TcHxAsO); and
trinorbornylarsine oxide for arsine As-oxides; and
hexamethylarsonamide; trimorpholinoarsine oxide;
tripiperidinoarsine oxide; tripyrrolidinoarsine oxide; and
tri(cyclohexylamino)arsine oxide for amino-substituted arsine
oxides. O Valence Stabilizer #36: Examples of cyanate ligands (O
monodentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
cyanate (--OCN). N--S Valence Stabilizer #1: Examples of
thioimidates, dithioimidates, polythioimidates, and derivatives of
thioimidic acid (N--S bidentates and N--S tetradentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: S-methyl
formathioimidate; S-ethyl formathioimidate; S-methyl
acetathioimidate; S-ethyl acetathioimidate; S-methyl
benzthioimidate; S-ethyl benzthioimidate; S-methyl
cyclohexylthioimidate; S-ethyl cyclohexylthioimidate; S-methyl
pentafluorobenzthioimidate; S-ethyl pentafluorobenzthioimidate;
S-methyl 2-pyridylthioimidate; S-ethyl 2-pyridylthioimidate;
S,S'-dimethyl benzdithioimidate; S,S'-dimethyl
tetrafluorobenzdithioimidate; 2-iminothiolane; and
2-iminotetrahydrothiopyran. [Note: Many thioimidate complexes are
decomposed by water, but their stability can be enhanced through
the use of fluorinated solubility control anions (e.g. PF.sub.6-).]
N--S Valence Stabilizer #2: Examples ofthioguanylureas,
guanidinothioureas, bis(thioguanylureas), bis(guanidinothioureas,
poly(thioguanylureas), and poly(guanidinothioureas) (N--S
Bidentates and N--S Tetradentates) that meet the requirements for
use as "narrow band" valence stabilizers for Co.sup.+3 include, but
are not limited to: thioguanylurea (amidinothiourea);
guanidinothiourea; methylthioguanylurea; ethylthioguanylurea;
isopropylthioguanylurea; butylthioguanylurea; benzylthioguanylurea;
phenylthioguanylurea; tolylthioguanylurea; naphthylthioguanylurea;
cyclohexylthioguanylurea; norbornylthioguanylurea;
adamantylthioguanylurea; dimethylthioguanylurea;
diethylthioguanylurea; diisopropylthioguanylurea;
dibutylthioguanylurea; dibenzylthioguanylurea;
diphenylthioguanylurea; ditolylthioguanylurea;
dinaphthylthioguanylurea; dicyclohexylthioguanylurea;
dinorbornylthioguanylurea; diadamantylthioguanylurea;
ethylenebis(thioguanylurea); propylenebis(thioguanylurea);
phenylenebis(thioguanylurea); piperazinebis(thioguanylurea);
oxalylbis(thioguanylurea); malonylbis(thioguanylurea);
succinylbis(thioguanylurea); and phthalylbis(thioguanylurea).
[Note: thioguanylureas generally tend to favor lower oxidation
states in complexed metals.] N--S Valence Stabilizer #3: Examples
of amidinothioamides, guanidinothioamides, bis(amidinothioamides),
bis(guanidinothioamides), poly(amidinothioamides), and
poly(guanidinothioamides) (including both N-amidinothioamides and
2-amidinothioacetamides) (N--S Bidentates, N--S Tridentates, and
N--S Tetradentates) that meet the requirements for use as "narrow
band" valence stabilizers for Co.sup.+3 include, but are not
limited to: amidinothioacetamide; guanidinothioamide,
amidinothiopropanamide; amidinothiobutanamide;
amidinothiobenzamide; amidinothiotoluamide;
amidinothiocyclohexamide; N-methylamidinothioacetamide;
N-ethylamidinothiopropanamide; N-propylamidinothiobutanamide;
N-phenylamidinothiobenzamide; N-tolylamidinothiotoluamide;
N-cyclohexylamidinothiocyclohexamide; bis(amidinothiooxamide);
bis(amidinothiomalonamide); bis(amidinothiosuccinamide);
bis(amidinothiophthalamide); 2-amidinothioacetamide
(thiomalonamamidine); N-methyl-2-amidinothioacetamide;
N-ethyl-2-amidinothioacetamide; N-phenyl-2-amidinothioacetamide;
N-benzyl-2-amidinothioacetamide;
N-cyclohexyl-2-amidinothioacetamide;
N,N'-dimethyl-2-amidinothioacetamide;
N,N'-diethyl-2-amidinothioacetamide;
N,N'-diphenyl-2-amidinothioacetamide;
N,N'-dibenzyl-2-amidinothioacetamide; and
N,N'-dicyclohexyl-2-amidinothioacetamide. [Note: amidinothioamides
generally tend to favor lower oxidation states in complexed
metals.] N--S Valence Stabilizer #4: Examples of imidoylthioamides,
bis(imidoylthioamides), and poly(imidoylthioamides) (N--S
Bidentates, N--S Tridentates, and N--S Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to:
acetimidoylthioacetamide; acetimidoylthiopropanamide;
acetimidoylthiobutanamide; acetimidoylthiobenzamide;
acetimidolylthiotoluamide; acetimidoylthiocyclohexamide;
propimidoylthiopropanamide; butimidoylthiobutanamide;
benzimidoylthiobenzamide; ethylenebis(acetimidoylthioacetamide);
propylenebis(acetimidoylthioacetamide); and
phenylenebis(acetimidoylthioacetamide). [Note: imidoylthioamides
generally tend to favor lower oxidation states in complexed
metals.] N--S Valence Stabilizer #5: Examples of thioureas,
bis(thioureas), and poly(thioureas), including thiourylene
complexes (N--S bidentates and N--S tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: thiourea;
methylthiourea; ethylthiourea; isopropylthiourea; benzylthiourea;
phenylthiourea; cyclohexylthiourea; naphthylthiourea (ntu);
biphenylthiourea; norbornylthiourea; adamantylthiourea;
N,N'-dimethylthiourea; N,N'-diethylthiourea;
N,N'-diisopropylthiourea; N,N'-dibenzylthiourea;
N,N'-dicyclohexylthiourea; N,N'dinapthylthiourea;
N,N'-dibiphenylthiourea; N,N'-dinorbornylthiourea;
N,N'-diadamantylthiourea; tetramethylthiourea; ethylenethiourea
(2-imidazolidinethione)(etu); 4,5-dihydroxy-2-imidazolinethione
(dhetu); propylenethiourea; N-(thiazol-2-yl)thiourea;
diphenylphosphinothioyl thioureas; allylthiourea;
N-allyl-N'-pyridylthiourea; N-allyl-N'-anisylthiourea;
N-allyl-N'-naphthylthiourea; N-allyl-N'-phenylthiourea;
thioglycoluril (acetylenethiourea); and bis(pyridylmethyl)thiourea.
[Note: thioureas generally tend to favor lower oxidation states in
complexed metals.] N--S Valence Stabilizer #6: Examples of
thiocarboxamides, bis(thiocarboxamides), and
poly(thiocarboxamides), (N--S bidentates, N--S tridentates, and
N--S tetradentates) that meet the requirements for use as "narrow
band" valence stabilizers for Co.sup.+3 include, but are not
limited to: thiocarbamide (tu); thioacetamide (taa);
thiopropionamide; thiobutanamide; thiobenzamide
(1-phenylthioformamide)(tba); 1-naphthylthioformamide;
1-cyclohexylthioformamide); 1-norbornylthioformamide;
1-adamantylthioformamide; N,N-dimethylthioformamide;
N,N-dimethylthioacetamide; pyridine-2-thiocarboxamide
(thiopicolinamide); pyrazine-2,3-dithiocarboxamide;
thionicotinamide; 2-thiophenethiocarboxamide;
N,N-dimethylthiobenzamide;
N-ethylthiocarbamide (N-etu); tetramethylthiocarbamide (tmtu);
2-thioacetamidothiazole (tatz); and polythioacrylamides. [Note:
thiocarboxamides generally tend to favor lower oxidation states in
complexed metals.] N--S Valence Stabilizer #7: Examples of
imidosulfurous diamides and bis(imidosulfurous diamides) (N--S
Bidentates, N--S Tridentates, and N--S Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to:
N,N'-diphenylimidosulfurous diamide; N,N'-dibenzylimidosulfurous
diamide; and phenylenebis(imidosulfurous diamide). [Note: These
complexes tend to hydrolyze unless stabilized with a fluorinated
anionic solubility control agent. The sulfite (S.sup.+4) valence of
the sulfur atom makes stabilizization of high valence metal ions
much more difficult, though still possible.] N--S Valence
Stabilizer #8: Examples of sulfurdiimines, bis(sulfurdiimines), and
poly(sulfurdiimines) (N--S Bidentates, N--S Tridentates, and N--S
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
N,N'-diphenylsulfurdiimine; N,N'-dibenzylsulfurdiimine; and
phenylenebis(sulfurdiimine). [Note: These complexes tend to
hydrolyze unless stabilized with a fluorinated anionic solubility
control agent. The sulfite (S.sup.+4) valence of the sulfur atom
makes stabilizization of high valence metal ions much more
difficult, though still possible.] N--S Valence Stabilizer #9:
Examples of phosphonimidothioic acid, phosphonimidodithioic acid,
bis(phosphonimidothioic acid); bis(phosphonimidodithioic acid), and
derivatives thereof (N--S Bidentates, N--S Tetradentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: phosphonimidothioic
acid, phosphonimidodithioic acid; O-phenylphosphonimidothioic acid;
O-benzylphosphonimidothioic acid; O-cyclohexylphosphonimidothioic
acid; O-norbornylphosphonimidothioic acid;
S-phenylphosphonimidodithioic acid; S-benzylphosphonimidodithioic
acid; S-cyclohexylphosphonimidodithioic acid; and
S-norbornylphosphonimidodithioic acid. [Note: The phosphite
(p.sup.+3) valence of the phosphorus atom makes stabilizization of
high valence metal ions much more difficult, though still
possible.] N--S Valence Stabilizer #10: Examples of phosphonothioic
diamides, bis(phosphonothioic diamides), and poly(phosphonothioic
diamides) (N--S Bidentates and N--S Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: phosphonothioic diamide,
phosphonothioic dihydrazide, phosphonamidothioic hydrazide,
N-phenylphosphonothioic diamide, N-benzylphosphonothioic diamide,
N-cyclohexylphosphonothioic diamide, and N-norbornylphosphonothioic
diamide. [Note: The phosphite (P.sup.+3) valence of the phosphorus
atom makes stabilizization of high valence metal ions much more
difficult, though still possible.] N--S Valence Stabilizer #1:
Examples of phosphonamidothioic acid, phosphonamidimidodithioic
acid, bis(phosphonamidothioic acid), bis(phosphonamidimidodithioic
acid), poly(phosphonamidothioic acid), and
poly(phosphonamidimidodithioic acid), and derivatives thereof (N--S
Bidentates and N--S Tetradentates) that meet the requirements for
use as "narrow band" valence stabilizers for Co.sup.+3 include, but
are not limited to: phosphonamidothioic acid,
phosphonamidimidodithioic acid, phosphonohydrazidodithioic acid,
phosphonohydrazidothioic acid, S-phenylphosphonamidimidodithioic
acid, S-benzylphosphonamidimidodithioic acid,
S-cyclohexylphosphonamidimidodithioic acid, and
S-norbornylphosphonamidimidodithioic acid. [Note: The phosphite
(p.sup.+3) valence of the phosphorus atom makes stabilizization of
high valence metal ions much more difficult, though still
possible.] N--S Valence Stabilizer #12: Examples of
beta-aminothiones (N-substituted 3-amino-2-propenethioaldehydes),
bis(beta-aminothiones), and poly(beta-aminothiones) (N--S
Bidentates and N--S Tetradentates) that meet the requirements for
use as "narrow band" valence stabilizers for Co.sup.+3 include, but
are not limited to: 4-methylamino-3-penten-2-thione;
4-ethylamino-3-penten-2-thione; 4-isopropylamino-3-penten-2-thione;
4-phenylamino-3-penten-2-thione; 4-naphthylamino-3-penten-2-thione;
4-cyclohexylamino-3-penten-2-thione;
4-norbornylamino-3-penten-2-thione;
4-hydroxyamino-3-penten-2-thione;
3-methylamino-1-phenyl-2-butenethioaldehydel;
3-ethylamino-1-phenyl-2-butenethioaldehyde;
3-isopropylamino-1-phenyl-2-butenethioaldehyde;
3-phenylamino-1-phenyl-2-butenethioaldehyde;
3-naphthylamino-1-phenyl-2-butenethioaldehyde;
3-cyclohexylamino-1-phenyl-2-butenethioaldehyde;
3-norbornylamino-1-phenyl-2-butenethioaldehyde;
3-hydroxyamino-1-phenyl-2-butenethioaldehyde;
3-phenylamino-1,3-diphenyl-2-propenethioaldehyde;
3-cyclohexylamino-1,3-dicyclohexyl-2-propenethioaldehyde; and
3-norbornylamino-1,3-dinorbornyl-2-propenethioaldehyde. N--S
Valence Stabilizer #13: Examples of 3-aminothioacrylamides
(3-amino-2-thiopropenamides), 3,3-diaminothioacrylamides,
bis(3-aminothioacrylamides), bis(3,3-diaminothioacrylamides),
poly(3-aminothioacrylamides), and poly(3,3-diaminothioacrylamides)
(N--S Bidentates and N--S Tetradentates) that meet the requirements
for use as "narrow band" valence stabilizers for Co.sup.+3 include,
but are not limited to: 3-methylaminothioacrylamide;
3-ethylaminothioacrylamide, 3-isopropylaminothioacrylamide,
3-phenylaminothioacrylamide; 3-naphthylaminothioacrylamide;
3-cyclohexylaminothioacrylamide; 3-norbornylaminothioacrylamide;
3-hydroxyaminothioacrylamide; N-methyl-3-methylaminothioacrylamide;
N-ethyl-3-ethylaminothioacrylamide,
N-isopropyl-3-isopropylaminothioacrylamide,
N-phenyl-3-phenylaminothioacrylamide;
N-naphthyl-3-naphthylaminothioacrylamide;
N-cyclohexyl-3-cyclohexylaminothioacrylamide;
N-norbornyl-3-norbornylaminothioacrylamide;
3-amino-3-methylaminothioacrylamide;
3-amino-3-ethylaminothioacrylamide,
3-amino-3-isopropylaminothioacrylamide,
3-amino-3-phenylaminothioacrylamide;
3-amino-3-naphthylaminothioacrylamide;
3-amino-3-cyclohexylaminothioacrylamide;
3-amino-3-norbornylaminothioacrylamide; and
3-amino-3-hydroxyaminothioacrylamide. N--S Valence Stabilizer #14:
Examples of 3-aminothioacrylic acids (3-amino-2-thiopropenoic
acids), 3-mercapto-3-aminothioacrylic acids, bis(3-aminothioacrylic
acids), bis(3-mercapto-3-aminothioacrylic acids),
poly(3-aminothioacrylic acids), and
poly(3-mercapto-3-aminothioacrylic acids), and derivatives thereof
(N--S Bidentates and N--S Tetradentates) that meet the requirements
for use as "narrow band" valence stabilizers for Co.sup.+3 include,
but are not limited to: 3-aminothioacrylic acid;
3-mercapto-3-aminothioacrylic acid; 3-methylaminothioacrylic acid;
3-ethylaminothioacrylic acid; 3-isopropylaminothioacrylic acid;
3-phenylaminothioacrylic acid; 3-naphthylaminothioacrylic acid;
3-cyclohexylaminothioacrylic acid; 3-norbornylaminothioacrylic
acid; 3-hydroxyaminothioacrylic acid; methyl
3-methylaminothioacrylate; ethyl 3-ethylaminothioacrylate;
isopropyl 3-isopropylaminothioacrylate; benzyl
3-phenylaminothioacrylate; naphthyl 3-naphthylaminothioacrylate;
cyclohexyl 3-cyclohexylaminothioacrylate; and norbornyl
3-norbornylaminothioacrylate. N--S Valence Stabilizer #15: Examples
of N-thioacyl benzylidenimines, bis(N-thioacyl benzylidenimines),
and poly(N-thioacyl benzylidenimines) (N--S Bidentates and N--S
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
N-thioformyl benzylidenimine, N-thioacetyl benzylidenimine;
N-thiobenzoyl benzylidenimine; and N-pentafluorothiobenzoyl
benzylidenimine. N--S Valence Stabilizer #16: Examples of
thiocarbonyl oximes, bis(thiocarbonyl oximes), and
poly(thiocarbonyl oximes) (N--S Bidentates, N--S Tridentates, and
N--S Tetradentates) that meet the requirements for use as "narrow
band" valence stabilizers for Co.sup.+3 include, but are not
limited to: butane-3-thione-2-one monoxime); and
diphenylethane-2-thione-1-one monoxime. N--S Valence Stabilizer
#17: Examples of mercapto oximes, bis(mercapto oximes), and
poly(mercapto oximes) (including 2-sulfurheterocyclic oximes) (N--S
Bidentates, N--S Tridentates, N--S Tetradentates, and N--S
Hexadentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
3-mercaptobutan-2-one oxime; 4-mercaptohexan-3-one oxime;
(1,2-diphenyl-2-mercaptoethanone oxime);
1,2-di(trifluoromethyl)-2-mercaptoethanone oxime;
1,2-dicyclohexyl-2-mercaptoethanone oxime;
1,2-dinorbornyl-2-mercaptoethanone oxime; 2-mercaptobenzaldehyde
oxime; 2-mercapto-1-naphthaldehyde oxime; thiophene-2-aldoxime;
methyl 2-thiophenyl ketoxime; and phenyl 2-thiophenyl ketoxime.
N--S Valence Stabilizer #18: Examples of 2-nitrothiophenols
(2-nitrobenzenethiols) (N--S Bidentates) that meet the requirements
for use as "narrow band" valence stabilizers for Co.sup.+3 include,
but are not limited to: 2-nitrothiophenol; 2,3-dinitrothiophenol;
2,4-dinitrothiophenol; 2,5-dinitrothiophenol;
2,6-dinitrothiophenol; 1-nitro-2-naphthalenethiol; and
2-nitro-1-naphthalenethiol. N--S Valence Stabilizer #19: Examples
of 2-nitrilothiophenols (2-nitrilobenzenethiols) (N--S Bidentates)
that meet the requirements for use as "narrow band" valence
stabilizers for Co.sup.+3 include, but are not limited to:
2-cyanothiophenol; 2,3-dicyanothiophenol; 2,4-dicyanothiophenol;
2,5-dicyanothiophenol; 2,6-dicyanothiophenol;
1-cyano-2-naphthalenethiol; and 2-cyano-1-naphthalenethiol. N--S
Valence Stabilizer #20: Examples of thiohydrazides,
bis(thiohydrazides), and poly(thiohydrazides) (N--S Bidentates and
N--S Tetradentates) that meet the requirements for use as "narrow
band" valence stabilizers for Co.sup.+3 include, but are not
limited to: thioformic hydrazide; thioacetic hydrazide;
thiopropionic hydrazide; thiobenzoic hydrazide;
thiophthalhydrazide; thiosalicylic hydrazide; thionaphthoic
hydrazides; thionorbornaneacetic hydrazide; thionicotinic
hydrazide; and thioisonicotinic hydrazide. [Note: Thiohydrazides
prefer complexation with lower oxidation states in metal ions.]
N--S Valence Stabilizer #21: Examples of thiosemicarbazides,
bis(thiosemicarbazides), and poly(thiosemicarbazides) (N--S
Bidentates, N--S Tetradentates, and N--S Hexadentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: thiosemicarbazide (tsc);
thiosemicarbazide diacetic acid (tsda); 1-methylthiosemicarbazide
(1 mts); 1-ethylthiosemicarbazide; 1-isopropylthiosemicarbazide;
1-phenylthiosemicarbazide (1 pts)(cryogenine);
1-benzylthiosemicarbazide; 1-cyclohexylthiosemicarbazide;
1-norbornylthiosemicarbazide; 4-methylthiosemicarbazide (4mts);
4-ethylthiosemicarbazide; 4-isopropylthiosemicarbazide;
4-phenylthiosemicarbazide (4-pts); 4-benzylthiosemicarbazide;
4-cyclohexylthiosemicarbazide; 4-norbornylthiosemicarbazide;
nicotinic thiosemicarbazide; isonicotinic thiosemicarbazide; and
4-phenyl-1-benzenesulfonyl-3-thiosemicarbazide (pbst). [Note:
Thiosemicarbazides prefer complexation with lower oxidation states
in metal ions.] N--S Valence Stabilizer #22: Examples of five-,
seven-, or nine-membered macrocyclics, macrobicyclics, and
macropolycyclics (including catapinands, cryptands, cyclidenes, and
sepulchrates) wherein all binding sites are composed of nitrogen
(usually amine or imine groups) or sulfur (usually thiols,
mercaptans, or thiocarbonyls) and are not contained in component
heterocyclic rings (N--S Tridentates, N--S Tetradentates, and N--S
Hexadentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
triazadithiacyclodecane ([10]aneS.sub.2N.sub.3);
triazadithiacycloundecane ([11]aneS.sub.2N.sub.3);
triazadithiacyclododecane ([12]aneS.sub.2N.sub.3);
triazadithiacyclotridecane ([13]aneS.sub.2N.sub.3);
triazadithiacyclotetradecane ([14]aneS.sub.2N.sub.3);
triazadithiacyclopentadecane ([15]aneS.sub.2N.sub.3);
thiomorpholine; and thiazolidine. N--S Valence Stabilizer #23:
Examples of five- or seven-membered macrocyclics, macrobicyclics,
and macropolycyclics (including catapinands, cryptands, cyclidenes,
and sepulchrates) wherein all binding sites are composed of
nitrogen or sulfur and are contained in component heterocyclic
rings (N--S Bidentates, N--S Tridentates, N--S Tetradentates, or
N--S Hexadentates) that meet the requirements for use as "narrow
band" valence stabilizers for Co.sup.+3 include, but are not
limited to: dithiopyrantripyridines; dithiophenetripyrroles;
trithiopyrantetrapyridines; and trithiophenetetrapyrroles. N--S
Valence Stabilizer #24: Examples of five-, seven-, or nine-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
binding sites are composed of nitrogen or sulfur and are contained
in a combination of heterocyclic rings and amine, imine, thiol,
mercapto, or thiocarbonyl groups (N--S Bidentates, N--S
Tridentates, N--S Tetradentates, or N--S Hexadentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: azathiapentaphyrins;
diazadithiapentaphyrins; azathiapentaphyrins; and
diazadithiapentaphyrins. N--O Valence Stabilizer #1: Examples of
imidates, diimidates, polyimidates, and derivatives of imidic acid
(N--O bidentates and N--O tetradentates) that meet the requirements
for use as "narrow band" valence stabilizers for Co.sup.+3 include,
but are not limited to: O-methyl formimidate; O-ethyl formimidate;
O-methyl acetimidate; O-ethyl acetimidate; O-methyl benzimidate;
O-ethyl benzimidate; O-methyl cyclohexylimidate; O-ethyl
cyclohexylimidate; O-methyl pentafluorobenzimidate; O-ethyl
pentafluorobenzimidate; O-methyl 2-pyridylimidate; O-ethyl
2-pyridylimidate; O,O'-dimethyl benzdiimidate; O,O'-dimethyl
tetrafluorobenzdiimidate; 2-iminotetrahydrofuran; and
2-iminotetrahydropyran. [Note: Most imidate complexes are
decomposed by water, but their stability can be enhanced through
the use of fluorinated solubility control anions (e.g.
PF.sub.6--).] N--O Valence Stabilizer #2: Examples ofpseudoureas,
bis(pseudoureas), and poly(pseudoureas) (N--O bidentates and N--O
tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
O-methyl pseudourea; O-ethyl pseudourea; O-isopropylpseudourea;
O-benzyl pseudourea; O-cyclohexyl pseudourea; O-norbornyl
pseudourea; O-pentafluorobenzyl pseudourea; N-methyl pseudourea;
N-ethyl pseudourea; N-isopropyl pseudourea; N-benzyl pseudourea;
N-cyclohexyl pseudourea; N-norbornyl pseudourea; and
N-pentafluorobenzyl pseudourea. N--O Valence Stabilizer #3:
Examples of 2-amidinoacetates, bis(2-amidinoacetates), and
poly(2-amidinoacetates) (N--O Bidentates and N--O Tetradentates)
that meet the requirements for use as "narrow band" valence
stabilizers for Co.sup.+3 include, but are not limited to:
N-methyl-2-amidinoacetate; O-methyl-2-amidinoacetate;
N-benzyl-2-amidinoacetate; and O-benzyl-2-amidinoacetate. [Note:
many 2-amidinoacetates tend to hydrolyze in water. This can be
minimized through the use of fluorinated solubility control anions
such as PF.sub.6--.] N--O Valence Stabilizer #4: Examples of ureas,
bis(ureas), and poly(ureas), including urylene complexes (N--O
bidentates and N--O tetradentates) that meet the requirements for
use as "narrow band" valence stabilizers for Co.sup.+3 include, but
are not limited to: urea; methylurea; ethylurea; isopropylurea;
benzylurea; cyclohexylurea; naphthylurea; biphenylurea;
norbornylurea; adamantylurea; N,N'-dimethylurea; N,N'-diethylurea;
N,N'-diisopropylurea; N,N'-dibenzylurea; N,N'-dicyclohexylurea;
N,N'dinapthylurea; N,N'-dibiphenylurea; N,N'-dinorbornylurea;
N,N'-diadamantylurea; ethyleneurea (2-imidazolidone);
propyleneurea; glycoluril (acetyleneurea); and
N,N'-bis(4-nitrophenyl)urea. N--O Valence Stabilizer #5: Examples
of phosphonimidic acid, bis(phosphonimidic acid),
poly(phosphonimidic acid), and derivatives thereof (N--O Bidentates
and N--O Tetradentates) that meet the requirements for use as
"narrow band" valence stabilizers for Co.sup.+3 include, but are
not limited to:
phosphonimidic acid; O-phenylphosphonimidic acid;
O-benzylphosphonimidic acid; O-cyclohexylphosphonimidic acid; and
O-norbornylphosphonimidic acid. [Note: The phosphite (P.sup.+3)
valence of the phosphorus atom makes stabilizization of high
valence metal ions much more difficult, though still possible.]
N--O Valence Stabilizer #6: Examples of phosphonamidic acid,
phosphonic diamide, bis(phosphonamidic acid), bis(phosphonic
diamide), poly(phosphonamidic acid), poly(phosphonic diamide), and
derivatives thereof (N--O Bidentates and N--O Tetradentates) that
meet the requirements for use as "narrow band" valence stabilizers
for Co.sup.+3 include, but are not limited to: phosphonamidic acid,
phosphonic diamide, phosphonamidic hydrazide, phosphonic
dihydrazide, O-phenylphosphonamidic acid, O-benzylphosphonamidic
acid, O-cyclohexylphosphonamidic acid, O-norbornylphosphonamidic
acid, N-benzylphosphonic diamide, N-phenylphosphonic diamide,
N-cyclohexylphosphonic diamide, and N-norbornylphosphonic diamide.
[Note: The phosphite (P.sup.+3) valence of the phosphorus atom
makes stabilizization of high valence metal ions much more
difficult, though still possible.] N--O Valence Stabilizer #7:
Examples of beta-ketoamines (N-substituted 3-amino-2-propenals),
bis(beta-ketoamines), and poly(beta-ketoamines) (N--O Bidentates
and N--O Tetradentates) that meet the requirements for use as
"narrow band" valence stabilizers for Co.sup.+3 include, but are
not limited to: 4-methylamino-3-penten-2-one;
4-ethylamino-3-penten-2-one; 4-isopropylamino-3-penten-2-one;
4-phenylamino-3-penten-2-one; 4-naphthylamino-3-penten-2-one;
4-cyclohexylamino-3-penten-2-one; 4-norbornylamino-3-penten-2-one;
4-hydroxyamino-3-penten-2-one; 3-methylamino-1-phenyl-2-butenal;
3-ethylamino-1-phenyl-2-butenal;
3-isopropylamino-1-phenyl-2-butenal;
3-phenylamino-1-phenyl-2-butenal;
3-naphthylamino-1-phenyl-2-butenal;
3-cyclohexylamino-1-phenyl-2-butenal;
3-norbornylamino-1-phenyl-2-butenal;
3-hydroxyamino-1-phenyl-2-butenal;
3-phenylamino-1,3-diphenyl-2-propenal;
3-cyclohexylamino-1,3-dicyclohexyl-2-propenal;
3-norbornylamino-1,3-dinorbornyl-2-propenal; 2,2'-pyridil;
alpha-pyridoin; 4-aminoantipyrine (aap);
beta-phenylaminopropiophenone; and polyaminoquinones (PAQs). N--O
Valence Stabilizer #8: Examples of 3-aminoacrylamides
(3-amino-2-propenamides), 3,3-diaminoacrylamides,
bis(3-aminoacrylamides), bis(3,3-diaminoacrylamides),
poly(3-aminoacrylamides), and poly(3,3-diaminoacrylamides) (N--O
Bidentates and N--O Tetradentates) that meet the requirements for
use as "narrow band" valence stabilizers for Co.sup.+3 include, but
are not limited to: 3-methylaminoacrylamide;
3-ethylaminoacrylamide, 3-isopropylaminoacrylamide,
3-phenylaminoacrylamide; 3-naphthylaminoacrylamide;
3-cyclohexylaminoacrylamide; 3-norbornylaminoacrylamide;
3-hydroxyaminoacrylamide; N-methyl-3-methylaminoacrylamide;
N-ethyl-3-ethylaminoacrylamide,
N-isopropyl-3-isopropylaminoacrylamide,
N-phenyl-3-phenylaminoacrylamide;
N-naphthyl-3-naphthylaminoacrylamide;
N-cyclohexyl-3-cyclohexylaminoacrylamide;
N-norbornyl-3-norbornylaminoacrylamide;
3-amino-3-methylaminoacrylamide; 3-amino-3-ethylaminoacrylamide,
3-amino-3-isopropylaminoacrylamide,
3-amino-3-phenylaminoacrylamide; 3-amino-3-naphthylaminoacrylamide;
3-amino-3-cyclohexylaminoacrylamide;
3-amino-3-norbornylaminoacrylamide; and
3-amino-3-hydroxyaminoacrylamide. N--O Valence Stabilizer #9:
Examples of 3-aminoacrylic acids (3-amino-2-propenoic acids),
3-hydroxy-3-aminoacrylic acids, bis(3-aminoacrylic acids),
bis(3-hydroxy-3-aminoacrylic acids), poly(3-aminoacrylic acids),
and poly(3-hydroxy-3-aminoacrylic acids), and derivatives
thereof(N--O Bidentates and N--O Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: 3-aminoacrylic acid;
3-hydroxy-3-aminoacrylic acid; 3-methylaminoacrylic acid;
3-ethylaminoacrylic acid; 3-isopropylaminoacrylic acid;
3-phenylaminoacrylic acid; 3-naphthylaminoacrylic acid;
3-cyclohexylaminoacrylic acid; 3-norbornylaminoacrylicacid;
3-hydroxyaminoacrylic acid; methyl 3-methylaminoacrylate; ethyl
3-ethylaminoacrylate; isopropyl 3-isopropylaminoacrylate; benzyl
3-phenylaminoacrylate; naphthyl 3-naphthylaminoacrylate; cyclohexyl
3-cyclohexylaminoacrylate; and norbornyl 3-norbornyl aminoacrylate.
N--O Valence Stabilizer #10: Examples ofN-acyl benzylidenimines,
bis(N-acyl benzylidenimines), and poly(N-acyl benzylidenimines)
(N--O Bidentates and N--O Tetradentates) that meet the requirements
for use as "narrow band" valence stabilizers for Co.sup.+3 include,
but are not limited to: N-formyl benzylidenimine, N-acetyl
benzylidenimine; N-benzoyl benzylidenimine; and
N-pentafluorobenzoyl benzylidenimine. N--O Valence Stabilizer #11:
Examples of 2-nitroanilines (N--O Bidentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: 2-nitroaniline;
2,6-dintroaniline; 2-nitrophenylenediamine;
2-nitrophenylenetriamine; 2-nitro-1-aminonaphthalene;
1-nitro-2-aminonaphthalene; nitrodiaminonaphthalene; and
dipicrylamine. N--O Valence Stabilizer #12: Examples of
2-nitrilophenols (N--O Bidentates) that meet the requirements for
use as "narrow band" valence stabilizers for Co.sup.+3 include, but
are not limited to: 2-cyanophenol; 2,3-dicyanophenol;
2,4-dicyanophenol; 2,5-dicyanophenol; 2,6-dicyanophenol;
1-cyano-2-naphthol; and 2-cyano-1-naphthol. Also includes
acylcyanamides. N--O Valence Stabilizer #13: Examples of amine
N-oxides and N-diazine oxides (azoxy compounds) (N--O Bidentates,
N--O Tridentates, and N--O Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: pyridine N-oxide (pyNO
or PNO); picoline N-oxide (picNO); lutidine N-oxide (lutNO or LNO);
collidine N-oxide (collNO or CNO); quinoline N-oxide (QuinNO or
QNO); isoquinoline N-oxide (isoQuinNO or IQNO); acridine N-oxide
(AcrNO or ANO); picolinic acid N-oxide (PicANO); pyridinethiolate
N-oxide (PTNO); adenine N-oxide; adenosine N-oxide;
1,10-phenanthroline mono-N-oxide (phenNO); 1,10-phenanthroline
N,N-dioxide (phen2NO); bipyridyl mono-N-oxide (bipyNO); bipyridyl
N,N-dioxide (bipy2NO); pyrazine mono-N-oxide (pyzNO); pyrazine
N,N-dioxide (pyz2NO); pyrimidine mono-N-oxide (pymNO); pyrimidine
N,N-dioxide (pym2NO); pyridazine mono-N-oxide (pdzNO); pyridazine
N,N-dioxide (pdz2NO); quinoxaline mono-N-oxide (qxNO); quinoxaline
N,N-dioxide (qx2NO); phenazine mono-N-oxide (phzNO); phenazine
N,N-dioxide (phz2NO); 2,3-di(pyridine N-oxide)quinoxaline (dpoq);
inosine N-oxide; 4,4'-bipyridine N,N-dioxide; 1-hydroxypyrazole
2-oxide; 1-hydroxyimidazole 3-oxide; 2,2'-diimidazyl 3,3'-dioxide;
imidazole N-oxides (1-hydroxyimidazole-3-N-oxides); N-benzylidine
aniline N-oxide; N-(naphthylidene) aniline N-oxide;
N-(hydroxybenzylidene) aniline N-oxide; and 2,2'-dibenzimidazyl
3,3'-dioxide (indigo N,N-dioxide) for amine N-oxides; and
azoxybenzene; phthalazine N-oxide; benzocinnoline N-oxide; and
bipyrazinyl N-oxide as N-diazine oxide examples. N--O Valence
Stabilizer #14: Examples of hydrazides, bis(hydrazides), and
poly(hydrazides) (N--O Bidentates and N--O Tetradentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: formic hydrazide; acetic
hydrazide; propionic hydrazide; benzoic hydrazide; phthalhydrazide;
salicylic hydrazide; naphthoic hydrazides; norbornaneacetic
hydrazide; nicotinic hydrazide; and isonicotinic hydrazide
(isoniazid). [Note: Hydrazides prefer complexation with lower
oxidation states in metal ions.] N--O Valence Stabilizer #15:
Examples of semicarbazides, bis(semicarbazides), and
poly(semicarbazides) (N--O Bidentates, N--O Tetradentates, and N--O
Hexadentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
semicarbazide (sc); semicarbazide diacetic acid (sda);
1-methylsemicarbazide; 1-ethylsemicarbazide;
1-isopropylsemicarbazide; 1-phenylsemicarbazide;
1-benzylsemicarbazide; 1-cyclohexylsemicarbazide;
1-norbornylsemicarbazide; 4-methylsemicarbazide;
4-ethylsemicarbazide; 4-isopropylsemicarbazide;
4-phenylsemicarbazide; 4-benzylsemicarbazide;
4-cyclohexylsemicarbazide; 4-norbornylsemicarbazide; nicotinic
semicarbazide; and isonicotinic semicarbazide. [Note:
Semicarbazides prefer complexation with lower oxidation states in
metal ions.] N--O Valence Stabilizer #16: Examples of five-,
seven-, or nine-membered macrocyclics, macrobicyclics, and
macropolycyclics (including catapinands, cryptands, cyclidenes, and
sepulchrates) wherein all binding sites are composed of nitrogen
(usually amine or imine groups) or oxygen (usually hydroxy,
carboxy, or carbonyl groups) and are not contained in component
heterocyclic rings (N--O Tridentates, N--O Tetradentates, and N--O
Hexadentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
triazadioxacyclodecane ([10]aneO.sub.2N.sub.3);
triazadioxacycloundecane ([11]aneO.sub.2N.sub.3);
triazadioxacyclododecane ([12]aneO.sub.2N.sub.3);
triazadioxacyclotridecane ([13]aneO.sub.2N.sub.3);
triazadioxacyclotetradecane ([14]aneO.sub.2N.sub.3); and
triazadioxacyclopentadecane ([15]aneO.sub.2N.sub.3). N--O Valence
Stabilizer #17: Examples offive- or seven-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all binding sites
are composed of nitrogen or oxygen and are contained in component
heterocyclic rings (N--O Bidentates, N--O Tridentates, N--O
Tetradentates, or N--O Hexadentates) that meet the requirements for
use as "narrow band" valence stabilizers for Co.sup.+3 include, but
are not limited to: dipyrantripyridines; difurantripyrroles;
tripyrantetrapyridines; and trifurantetrapyrroles. N--O Valence
Stabilizer #18: Examples of five-, seven-, or nine-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
binding sites are composed of nitrogen or oxygen and are contained
in a combination of heterocyclic rings and amine, imine, hydroxy,
carboxy, or carbonyl groups (N--O Bidentates, N--O Tridentates,
N--O Tetradentates, or N--O Hexadentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: azaoxapentaphyrins;
diazadioxapentaphyrins; azaoxapentaphyrins; and
diazadioxapentaphyrins. S--O Valence Stabilizer #1: Examples of
thiobiurets (thioimidodicarbonic diamides), thioisobiurets,
thiobiureas, thiotriurets, thiotriureas, bis(thiobiurets),
bis(thioisobiurets), bis(thiobiureas), poly(thiobiurets),
poly(thioisobiurets), and poly(thiobiureas) (S--O Bidentates, S--O
Tridentates, S--O Tetradentates) that meet the requirements for use
as "narrow band" valence stabilizers for Co.sup.+3 include, but are
not limited to: thiobiuret, thioisobiuret, thiobiurea, thiotriuret,
thiotriurea, nitrothiobiuret, dinitrothiobiuret, aminothiobiuret,
diaminothiobiuret, oxythiobiuret, dioxythiobiuret, cyanothiobiuret,
methylthiobiuret, ethylthiobiuret, isopropylthiobiuret,
phenylthiobiuret, benzylthiobiuret, cyclohexylthiobiuret,
norbornylthiobiuret, adamantylthiobiuret, dimethylthiobiuret,
diethylthiobiuret, diisopropylthiobiuret, diphenylthiobiuret,
dibenzylthiobiuret, dicyclohexylthiobiuret, dinorbornylthiobiuret,
diadamantylthiobiuret' and 3-formamidino thiocarbamides. S--O
Valence Stabilizer #2: Examples of acylthioureas, aroylthioureas,
thioacylureas, thioaroylureas, bis(acylthioureas),
bis(aroylthioureas), bis(thioacylureas), bis(thioaroylureas),
poly(thioacylthioureas), poly(thioaroylthioureas),
poly(thioacylureas), and poly(thioaroylureas) (S--O Bidentates,
S--O Tridentates, S--O Tetradentates) that meet the requirements
for use as "narrow band" valence stabilizers for Co.sup.+3 include,
but are not limited to: thioformylurea, thioacetylurea,
thiobenzoylurea, thiocyclohexoylurea, pentafluorothiobenzoylurea,
acetylthiourea, benzoylthiourea, and cyclohexoylthiourea. S--O
Valence Stabilizer#3: Examples ofthioimidodialdehydes,
thiohydrazidodialdehydes (thioacyl hydrazides),
bis(thioimidodialdehydes), bis(thiohydrazidodialdehydes),
poly(thioimidodialdehydes), and poly(thiohydrazidodialdehydes)
(S--O Bidentates, S--O Tridentates, S--O Tetradentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: thiodiacetamide,
thiodipropanamide, thiodibutanamide, thiodibenzamide, and
thiodicyclohexamide. S--O Valence Stabilizer #4: Examples
ofthioimidodicarbonic acids, thiohydrazidodicarbonic acids,
bis(thioimidodicarbonic acids), bis(thiohydrazidodicarbonic acids),
poly(thioimidodicarbonic acids), poly(thiohydrazidodicarbonic
acids) and derivatives thereof (S--O Bidentates, S--O Tridentates,
S--O Tetradentates) that meet the requirements for use as "narrow
band" valence stabilizers for Co.sup.+3 include, but are not
limited to: thioimidodicarbonic acid, thiohydrazidodicarbonic acid,
O-phenylthioimidodicarbonic acid, O-benzylthioimidodicarbonic acid,
O-cyclohexylthioimidodicarbonic acid,
O-norbornylthioimidodicarbonic acid,
O,O'-diphenylthioimidodicarbonic acid,
O,O'-dibenzylthioimidodicarbonic acid,
O,O'-dicyclohexylthioimidodicarbonic acid,
O,O'-dinorbornylthioimidodicarbonic acid. S--O Valence Stabilizer
#5: Examples of 1,2-monothioketones (monothiolenes,
monothio-alpha-ketonates), 1,2,3-monothioketones,
1,2,3-dithioketones, monothiotropolonates, ortho-monothioquinones,
bis(1,2-monothioketones), and poly(1,2-monothioketones) (S--O
Bidentates, S--O Tridentates, S--O Tetradentates) that meet the
requirements for use as "narrow band" valence slabilizers for
Co.sup.+3 include, but are not limited to: monothiotropolone;
1,2-monothiobenzoquinone (o-monothioquinone);
di-tert-butyl-1,2-monothiobenzoquinone;
hexafluoro-1,2-monothiobenzoquinone; 1,2-monothionaphthoquinone;
9,10-monothiophenanthroquinone; monothiosquaric acid;
monothiodeltic acid; monothiocroconic acid; and monothiorhodizonic
acid. S--O Valence Stabilizer #6: Examples of
trithioperoxydicarbonic diamides, bis(trithioperoxydicarbonic
diamides), and poly(trithioperoxydicarbonic diamides) (S--O
Bidentates, S--O Tridentates, S--O Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: trithioperoxydicarbonic
diamide; N-phenyltrithioperoxydicarbonic diamide;
N-benzyltrithioperoxydicarbonic diamide;
N-cyclohexyltrithioperoxydicarbonic diamide;
N-norbornyltrithioperoxydicarbonic diamide;
N,N'-diphenyltrithioperoxydicarbonic diamide;
N,N'-dibenzyltrithioperoxydicarbonic diamide;
N,N'-dicyclohexyltrithioperoxydicarbonic diamide; and
N,N'-dinorbornyltrithioperoxydicarbonic diamide. S--O Valence
Stabilizer #7: Examples of dithiodicarbonic acids,
bis(dithiodicarbonic acids), poly(dithiodicarbonic acids), and
derivatives thereof (S--O Bidentates, S--O Tridentates, S--O
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
dithiodicarbonic acid, O-phenyldithiodicarbonic acid,
O-benzyldithiodicarbonic acid, O-cyclohexyldithiodicarbonic acid,
O-norbornyldithiodicarbonic acid, O,O'-diphenyldithiodicarbonic
acid, O,O'-dibenzyldithiodicarbonic acid,
O,O'-dicyclohexyldithiodicarbonic acid, and
O,O'-dinorbornyldithiodicarbonic acid. S--O Valence Stabilizer #8:
Examples oftrithioperoxydicarbonic acids,
bis(trithioperoxydicarbonic acids), poly(trithioperoxydicarbonic
acids), and derivatives thereof (S--O Bidentates, S--O Tridentates,
S--O Tetradentates) that meet the requirements for use as "narrow
band" valence stabilizers for Co.sup.+3 include, but are not
limited to: trithioperoxydicarbonic acid,
O-phenyltrithioperoxydicarbonic acid;
O-benzyltrithioperoxydicarbonic acid;
O-cyclohexyltrithioperoxydicarbonic acid;
O-norbornyltrithioperoxydicarbonic acid;
O,O'-diphenyltrithioperoxydicarbonic acid;
O,O'-dibenzyltrithioperoxydicarbonic acid;
O,O'-dicyclohexyltrithioperoxydicarbonic acid; and
O,O'-dinorbornyltrithioperoxydicarbonic acid. S--O Valence
Stabilizer #9: Examples of monothioperoxydiphosphoramides,
bis(monothioperoxydiphosphoramides), and
poly(monothioperoxydiphosphoramides) (S--O Bidentates, S--O
Tridentates, S--O Tetradentates) that meet the requirements for use
as "narrow band" valence stabilizers for Co.sup.+3 include, but are
not limited to: monothioperoxydiphosphoramide,
N-methylmonothioperoxydiphosphoramide,
N-isopropylmonothioperoxydiphosphoramide,
N-tert-butylmonothioperoxydiphosphoramide,
N-phenylmonothioperoxydiphosphoramide,
N-pentafluorophenylmonothioperoxydiphosphoramide,
N-benzylmonothioperoxydiphosphoramide,
N-cyclohexylmonothioperoxydiphosphoramide,
N-norbornylmonothioperoxydiphosphoramide,
N,N'''-dimethylmonothioperoxydiphosphoramide,
N,N'''-diisopropylmonothioperoxydiphosphoramide,
N,N'''-di-tert-butylmonothioperoxydiphosphoramide,
N,N'''-diphenylmonothioperoxydiphosphoramide,
N,N'''-dipentafluorophenylmonothioperoxydiphosphoramide,
N,N'''-dibenzylmonothioperoxydiphosphoramide,
N,N'''-dicyclobexylmonothioperoxydiphosphoramide, and
N,N'''-dinorbornylmonothioperoxydiphosphoramide. S--O Valence
Stabilizer #10: Examples of monothioperoxydiphosphoric acids,
bis(monothioperoxydiphosphoric acids),
poly(monothioperoxydiphosphoric acids), and derivatives thereof
(S--O Bidentates, S--O Tridentates, S--O Tetradentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to:
monothioperoxydiphosphoric acid, methylmonothioperoxydiphosphoric
acid, isopropylmonothioperoxydiphosphoric acid,
tert-butylmonothioperoxydiphosphoric acid,
phenylmonothioperoxydiphosphoric acid,
pentafluorophenylmonothioperoxydiphosphoric acid,
benzylmonothioperoxydiphosphoric acid,
cyclohexylmonothioperoxydiphosphoric acid,
norbornylmonothioperoxydiphosphoric acid,
dimethylmonothioperoxydiphosphoric acid,
diisopropylmonothioperoxydiphosphoric acid,
di-tert-butylmonothioperoxydiphosphoric acid,
diphenylmonothioperoxydiphosphoric acid,
di-pentafluorophenylmonothioperoxydiphosphoric acid,
dibenzylmonothioperoxydiphosphoric acid,
dicyclohexylmonothioperoxydiphosphoric acid, and
dinorbornylmonothioperoxydiphosphoric acid. S--O Valence Stabilizer
#11: Examples of monothioimidodiphosphonic acids,
monothiohydrazidodiphosphonic acids, bis(monothioimidodiphosphonic
acids), bis(monothiohydrazidodiphosphonic acids),
poly(monothioimidodiphosphonic acids),
poly(monothiohydrazidodiphosphonic acids), and derivatives thereof
(S--O Bidentates, S--O Tridentates, S--O Tetradentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to:
monothioimidodiphosphonic acid, methylmonothioimidodiphosphonic
acid, isopropylmonothioimidodiphosphonic acid,
tert-butylmonothioimidodiphosphonic acid,
phenylmonothioimidodiphosphonic acid,
pentafluorophenylmonothioimidodiphosphonic acid,
benzylmonothioimidodiphosphonic acid,
cyclohexylmonothioimidodiphosphonic acid,
norbornylmonothioimidodiphosphonic acid,
dimethylmonothioimidodiphosphonic acid,
diisopropylmonothioimidodiphosphonic acid,
di-tert-butylmonothioimidodiphosphonic acid,
diphenylmonothioimidodiphosphonic acid,
di-pentafluorophenylmonothioimidodiphosphonic acid,
dibenzylmonothioimidodiphosphonic acid,
dicyclohexylmonothioimidodiphosphonic acid, and
dinorbornylmonothioimidodiphosphonic acid. [Note: The phosphite
(P.sup.+3) valence of the phosphorus atom makes stabilizization of
high valence metal ions much more difficult, though still
possible.] S--O Valence Stabilizer #12: Examples of
monothioimidodiphosphonamides, monothiohydrazidodiphosphonamides,
bis(monothioimidodiphosphonamides),
bis(monothiohydrazidodiphosphonamides),
poly(monothioimidodiphosphonamides), and
poly(monothiohydrazidodiphosphonamides) (S--O Bidentates, S--O
Tridentates, S--O Tetradentates) that meet the requirements for use
as "narrow band" valence stabilizers for Co.sup.+3 include, but are
not limited to: monothioimidodiphosphonamide,
N-methylmonothioimidodiphosphonamide,
N-isopropylmonothioimidodiphosphonamide,
N-tert-butylmonothioimidodiphosphonamide,
N-phenylmonothioimidodiphosphonamide,
N-pentafluorophenylmonothioimidodiphosphonamide,
N-benzylmonothioimidodiphosphonamide,
N-cyclohexylmonothioimidodiphosphonamide,
N-norbornylmonothioimidodiphosphonamide,
N,N'''-dimethylmonothioimidodiphosphonamide,
N,N'''-diisopropylmonothioimidodiphosphonamide,
N,N'''-di-tert-butylmonothioimidodiphosphonamide,
N,N'''-diphenylmonothioimidodiphosphonamide,
N,N'''-di-pentafluorophenylmonothioimidodiphosphonamide,
N,N'''-dibenzylmonothioimidodiphosphonamide,
N,N'''-dicyclohexylmonothioimidodiphosphonamide, and
N,N'''-dinorbornylmonothioimidodiphosphonamide. [Note: The
phosphite (P.sup.+3) valence of the phosphorus atom makes
stabilizization of high valence metal ions much more difficult,
though still possible.] S--O Valence Stabilizer #13: Examples of
dithiodiphosphonamides, bis(dithiodiphosphonamides), and
poly(dithiodiphosphonamides) (S--O Bidentates, S--O Tridentates,
S--O Tetradentates) that meet the requirements for use as "narrow
band" valence stabilizers for Co.sup.+3 include, but are not
limited to: dithiodiphosphonamide, N-methyldithiodiphosphonamide,
N-isopropyldithiodiphosphonamide,
N-tert-butyldithiodiphosphonamide, N-phenyldithiodiphosphonamide,
N-pentafluorophenyldithiodiphosphonamide,
N-benzyldithiodiphosphonamide, N-cyclohexyldithiodiphosphonamide,
N-norbornyldithiodiphosphonamide,
N,N'''-dimethyldithiodiphosphonamide,
N,N'''-diisopropyldithiodiphosphonamide,
N,N'''-di-tert-butyldithiodiphosphonamide,
N,N'''-diphenyldithiodiphosphonamide,
N,N'''-di-pentafluorophenyldithiodiphosphonamide,
N,N'''-dibenzyldithiodiphosphonamide,
N,N'''-dicyclohexyldithiodiphosphonamide, and
N,N'''-dinorbornyldithiodiphosphonamide. [Note: The phosphite
(P.sup.+3) valence of the phosphorus atom makes stabilizization of
high valence metal ions much more difficult, though still
possible.] S--O Valence Stabilizer#14: Examples of
dithiodiphosphonic acids, bis(dithiodiphosphonic acids),
poly(dithiodiphosphonic acids), and derivatives thereof (S--O
Bidentates, S--O Tridentates, S--O Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: dithiodiphosphonic acid,
methyldithiodiphosphonic acid, isopropyldithiodiphosphonic acid,
tert-butyldithiodiphosphonic acid, phenyldithiodiphosphonic acid,
pentafluorophenyldithiodiphosphonic acid, benzyldithiodiphosphonic
acid, cyclohexyldithiodiphosphonic acid,
norbornyldithiodiphosphonic acid, dimethyldithiodiphosphonic acid,
diisopropyldiothiodiphosphonic acid,
di-tert-butyldithiodiphosphonic acid, diphenyldithiodiphosphonic
acid, di-pentafluorophenyldithiodiphosphonic acid,
dibenzyldithiodiphosphonic acid, dicyclohexyldithiodiphosphonic
acid, and dinorbornyldithiodiphosphoric acid. [Note: The phosphite
(P.sup.+3) valence of the phosphorus atom makes stabilizization of
high valence metal ions much more difficult, though still
possible.] S--O Valence Stabilizer #15: Examples of
monothioperoxydiphosphonamides, bi
s(monothioperoxydiphosphonamides), and
poly(monothioperoxydiphosphonamides) (S--O Bidentates, S--O
Tridentates, S--O Tetradentates) that meet the requirements for use
as "narrow band" valence stabilizers for Co.sup.+3 include, but are
not limited to: monothioperoxydiphosphonamide,
N-methylmonothioperoxydiphosphonamide,
N-isopropylmonothioperoxydiphosphonamide,
N-tert-butylmonothioperoxydiphosphonamide,
N-phenylmonothioperoxydiphosphonamide,
N-pentafluorophenylmonothioperoxydiphosphonamide,
N-benzylmonothioperoxydiphosphonamide,
N-cyclohexylmonothioperoxydiphosphonamide,
N-norbornylmonothioperoxydiphosphonamide,
N,N'''-dimethylmonothioperoxydiphosphonamide,
N,N'''-diisopropylmonothioperoxydiphosphonamide,
N,N'''-di-tert-butylmonothioperoxydiphosphonamide,
N,N'''-diphenylmonothioperoxydiphosphonamide,
N,N'''-di-pentafluorophenylmonothioperoxydiphosphonamide,
N,N'''-dibenzylmonothioperoxydiphosphonamide,
N,N'''-dicyclohexylmonothioperoxydiphosphonamide, and
N,N'''-dinorbornylmonothioperoxydiphosphonamide. [Note: The
phosphite (P.sup.+3) valence of the phosphorus atom makes
stabilizization of high valence metal ions much more difficult,
though still possible.] S--O Valence Stabilizer #16: Examples of
monothioperoxydiphosphonic acids, bis(monothioperoxydiphosphonic
acids), poly(monothioperoxydiphosphonic acids), and derivatives
thereof (S--O Bidentates, S--O Tridentates, S--O Tetradentates)
that meet the requirements for use as "narrow band" valence
stabilizers for Co.sup.+3 include, but are not limited to:
monothioperoxydiphosphonic acid, methylmonothioperoxydiphosphonic
acid, isopropylmonothioperoxydiphosphonic acid,
tert-butylmonothioperoxydiphosphonic acid,
phenylmonothioperoxydiphosphonic acid,
pentafluorophenylmonothioperoxydiphosphonic acid,
benzylmonothioperoxydiphosphonic acid,
cyclohexylmonothioperoxydiphosphonic acid,
norbornylmonothioperoxydiphosphonic acid,
dimethylmonothioperoxydiphosphonic acid,
diisopropylmonothioperoxydiphosphonic acid,
di-tert-butylmonothioperoxydiphosphonic acid,
diphenylmonothioperoxydiphosphonic acid,
di-pentafluorophenylmonothioperoxydiphosphonic acid,
dibenzylmonothioperoxydiphosphonic acid,
dicyclohexylmonothioperoxydiphosphonic acid, and
dinorbornylmonothioperoxydiphosphonic acid. [Note: The phosphite
(P.sup.+3) valence of the phosphorus atom makes stabilizization of
high valence metal ions much more difficult, though still
possible.] S--O Valence Stabilizer #17: Examples of
monothiophosphoric acids (phosphorothioic acids),
bis(monothiophosphoric acids), poly(monothiophosphoric acids), and
derivatives thereof (S--O Bidentates, S--O Tridentates, S--O
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
monothiophosphoric acid, O-phenylmonothiophosphoric acid,
O-benzylmonothiophosphoric acid, O-cyclohexylmonothiophosphoric
acid, O-norbornylmonothiophosphoric acid,
O,O-diphenylmonothiophosphoric acid, O,O-dibenzylmonothiophosphoric
acid, O,O-dicyclohexylmonothiophosphoric acid, and
O,O-dinorbornylmonothiophosphoric acid. S--O Valence Stabilizer
#18: Examples of phosphoro(dithioperoxoic) acids,
bis[phosphoro(dithioperoxoic) acids],
poly[phosphoro(dithioperoxoic) acids], and derivatives thereof
(S--O Bidentates, S--O Tridentates, S--O Tetradentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to:
phosphoro(dithioperoxoic) acid, O-phenylphosphoro(dithioperoxoic)
acid, O-benzylphosphoro(dithioperoxoic) acid,
O-cyclohexylphosphoro(dithioperoxoic) acid,
O-norbornylphosphoro(dithioperoxoic) acid,
O,O-diphenylphosphoro(dithioperoxoic) acid,
O,O-dibenzylphosphoro(dithioperoxoic) acid,
O,O-dicyclohexylphosphoro(dithioperoxoic) acid, and
O,O-dinorbornylphosphoro(dithioperoxoic) acid. S--O Valence
Stabilizer #19: Examples of monothiophosphonic Acids
(phosphonothioic acids), bis(monothiophosphonic acids),
poly(monothiophosphonic acids), and derivatives thereof (S--O
Bidentates, S--O Tridentates, S--O Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: monothiophosphonic acid,
O-phenylmonothiophosphonic acid, O-benzylmonothiophosphonic acid,
O-cyclohexylmonothiophosphonic acid, O-norbornylmonothiophosphonic
acid, O,P-diphenylmonothiophosphonic acid,
O,P-dibenzylmonothiophosphonic acid,
O,P-dicyclohexylmonothiophospbonic acid, and
O,P-dinorbornylmonothiophosphonic acid. [Note: The phosphite
(P.sup.+3) valence of the phosphorus atom makes stabilizization of
high valence metal ions much more difficult, though still
possible.] S--O Valence Stabilizer #20: Examples of
phosphono(dithioperoxoic) acids, bis[phosphono(dithioperoxoic)
acids], poly[phosphono(dithioperoxoic) acids], and derivatives
thereof (S--O Bidentates, S--O Tridentates, S--O Tetradentates)
that meet the requirements for use as "narrow band" valence
stabilizers for Co.sup.+3 include, but are not limited to:
phosphono(dithioperoxoic) acid, O-phenylphosphono(dithioperoxoic)
acid, O-benzylphosphono(dithioperoxoic) acid,
O-cyclohexylphosphono(dithioperoxoic) acid,
O-norbornylphosphono(dithioperoxoic) acid,
O,P-diphenylphosphono(dithioperoxoic) acid,
O,P-dibenzylphosphono(dithioperoxoic) acid,
O,P-dicyclohexylphosphono(dithioperoxoic) acid, and
O,P-dinorbornylphosphono(dithioperoxoic) acid. [Note: The phosphite
(P.sup.+3) valence of the phosphorus atom makes stabilizization of
high valence metal ions much more difficult, though still
possible.] S--O Valence Stabilizer #21: Examples of
beta-hydroxythioketones, beta-hydroxythioaldehydes,
bis(beta-hydroxythioketones), bis(beta-hydroxythioaldehydes),
poly(beta-hydroxythioketones), and poly(beta-hydroxythioaldehydes)
(S--O Bidentates, S--O Tridentates, S--O Tetradentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to:
4-hydroxypentan-2-thione;
1,3-diphenyl-3-hydroxypropanethioaldehyde;
1,3-dibenzyl-3-hydroxypropanethioaldehyde;
1,3-dicyclohexyl-3-hydroxypropanethioaldehyde;
1,3-dinorbornyl-3-hydroxypropanethioaldehyde;
1,3-di(2-thienyl)-3-hydroxypropanethioaldehyde;
1,3-di(2-furyl)-3-hydroxypropanethioaldehyde;
o-hydroxythioacetophenone; and beta-hydroxythiobenzophenone. S--O
Valence Stabilizer #22: Examples ofbeta-mercaptoketones,
beta-mercaptoaldehydes, bis(beta-mercaptoketones),
bis(beta-mercaptoaldehydes), poly(beta-mercaptoketones), and
poly(beta-mercaptoaldehydes) (S--O Bidentates, S--O Tridentates,
S--O Tetradentates) that meet the requirements for use as "narrow
band" valence stabilizers for Co.sup.+3 include, but are not
limited to: 4-mercaptopentan-2-one;
1,3-diphenyl-3-mercaptopropanal; 1,3-dibenzyl-3-mercaptopropanal;
1,3-dicyclohexyl-3-mercaptopropanal;
1,3-dinorbornyl-3-mercaptopropanal;
1,3-di(2-thienyl)-3-mercaptopropanal;
1,3-di(2-furyl)-3-mercaptopropanal;
3-mercapto-1,5-pentanedialdehyde; o-mercaptoacetophenone;
5-mercapto-1,4-naphthoquinone; 1-mercaptoacridone;
1-mercaptoanthraquinone; 1,8-dimercaptoanthraquinone; and
beta-mercaptobenzophenone. S--O Valence Stabilizer #23: Examples of
N-(aminomethylol)thioureas [N-(aminohydroxymethyl)thioureas],
bis[N-(aminomethylol)thioureas], and
poly[N-(aminomethylol)thioureas] (S--O Bidentates, S--O
Tridentates, S--O Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to:
N'-(aminohydroxymethyl)thiourea;
N,N''-dimethyl-N'-(aminohydroxymethyl)thiourea;
N,N'-diethyl-N'-(aminohydroxymethyl)thiourea;
N,N''-isopropyl-N'-(aminohydroxymethyl)thiourea;
N,N''-diphenyl-N'-(aminohydroxymethyl)thiourea;
N,N''-dibenzyl-N'-(aminohydroxymethyl)thiourea;
N,N''-dicyclohexyl-N'-(aminohydroxymethyl)thiourea; and
N,N''-dinorbornyl-N'-(aminohydroxymethyl)thiourea. S--O Valence
Stabilizer #24: Examples of N-(aminomethylthiol)ureas
[N-(aminomercaptomethyl)ureas], bis[N-(aminomethylthiol)ureas], and
poly[N-(aminomethylthiol)ureas] (S--O Bidentates, S--O Tridentates,
S--O Tetradentates) that meet the requirements for use as "narrow
band" valence stabilizers for Co.sup.+3 include, but are not
limited to: N'-(aminomercaptomethyl)urea;
N,N''-dimethyl-N'-(aminomercaptomethyl)urea;
N,N'-diethyl-N'-(aminomercaptomethyl)urea;
N,N''-isopropyl-N'-(aminomercaptomethyl)urea;
N,N''-diphenyl-N'-(aminomercaptomethyl)urea;
N,N''-dibenzyl-N'-(aminomercaptomethyl)urea;
N,N''-dicyclohexyl-N'-(aminomercaptomethyl)urea; and
N,N''-dinorbornyl-N'-(aminomercaptomethyl)urea. S--O Valence
Stabilizer #25: Examples of monothiooxamides,
bis(monothiooxamides), and poly(monothiooxamides) (S--O Bidentates,
S--O Tridentates, S--O Tetradentates) that meet the requirements
for use as "narrow band" valence stabilizers for Co.sup.+3 include,
but are not limited to: monothiooxamide, N-methylthiooxamide;
N-ethylthiooxamide; N-isopropylthiooxamide; N-phenylthiooxamide;
N-benzylthiooxamide; N-cyclohexylthiooxamide;
N-norbornylthiooxamide; N,N'-dimethylthiooxamide;
N,N'-diethylthiooxamide; N,N'-diisopropylthiooxamide;
N,N'-diphenylthiooxamide; N,N'-dibenzylthiooxamide;
N,N'-dicyclohexylthiooxamide; and N,N'-dinorbornylthiooxamide. S--O
Valence Stabilizer #26: Examples of beta-mercapto carboxylic acids,
bis(beta-mercapto carboxylic acids), poly(beta-mercapto carboxylic
acids), and derivatives thereof (S--O Bidentates, S--O Tridentates,
S--O Tetradentates) that meet the requirements for use as "narrow
band" valence stabilizers for Co.sup.+3 include, but are not
limited to: methyl 3-mercaptopropanoate; methyl
3-mercaptobutanoate; ethyl 3-mercaptobutanoate; phenyl
3-mercaptobutanoate; cyclohexyl 3-mercaptobutanoate; norbornyl
3-mercaptobutanoate; methyl beta-mercaptohydrocinnamate; ethyl
beta-mercaptohydrocinnamate; phenyl beta-mercaptohydrocinnamate;
methyl o-mercaptobenzoate; ethyl o-mercaptobenzoate; phenyl
o-mercaptobenzoate; cyclohexyl o-mercaptobenzoate;
(2-benzothiazolylthio) succinic acid (mtbs); norbornyl
o-mercaptobenzoate; and 3-[(benzothiazol-2-yl)thio]propionic acid.
S--O Valence Stabilizer #27: Examples of beta-mercapto
thiocarboxylic acids, bis(beta-mercapto thiocarboxylic acids),
poly(beta-mercapto thiocarboxylic acids), and derivatives thereof
(S--O Bidentates, S--O Tridentates, S--O Tetradentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: methyl
3-mercaptothiobutanoate; ethyl 3-mercaptothiobutanoate; phenyl
3-mercaptothiobutanoate; cyclohexyl 3-mercaptothiobutanoate;
norbornyl 3-mercaptothiobutanoate; methyl
beta-mercaptothiocinnamate; ethyl beta-mercaptothiocinnamate;
phenyl beta-mercaptothiocinnamate; methyl o-mercaptothiobenzoate;
ethyl o-mercaptothiobenzoate; phenyl o-mercaptothiobenzoate;
cyclohexyl o-mercaptothiobenzoate; norbornyl
o-mercaptothiobenzoate; and (alkylthio)oxoethyl alkyl(aryl)
disulfides. S--O Valence Stabilizer #28: Examples of beta-hydroxy
thiocarboxylic acids, bis(beta-hydroxy thiocarboxylic acids),
poly(beta-hydroxy thiocarboxylic acids), and derivatives thereof
(S--O Bidentates, S--O Tridentates, S--O Tetradentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: methyl
3-hydroxythiobutanoate; ethyl 3-hydroxythiobutanoate; phenyl
3-hydroxythiobutanoate; cyclohexyl 3-hydroxythiobutanoate;
norbornyl 3-hydroxythiobutanoate; methyl beta-hydroxythiocinnamate;
ethyl beta-hydroxythiocinnamate; phenyl beta-hydroxythiocinnamate;
methyl o-hydroxythiobenzoate; ethyl o-hydroxythiobenzoate; phenyl
o-hydroxythiobenzoate; cyclohexyl o-hydroxythiobenzoate; and
norbornyl o-hydroxythiobenzoate. S--O Valence Stabilizer #29:
Examples of beta-mercapto carboxamides, bis(beta-mercapto
carboxamides), poly(beta-mercapto carboxamides), and derivatives
thereof (S--O Bidentates, S--O Tridentates, S--O Tetradentates)
that meet the requirements for use as "narrow band" valence
stabilizers for Co.sup.+3 include, but are not limited to: N-methyl
3-mercaptobutanamide; N-ethyl 3-mercaptobutanamide; N-phenyl
3-mercaptobutanamide; N-cyclohexyl 3-mercaptobutanamide;
N-norbornyl 3-mercaptobutanamide; N-methyl o-mercaptobenzamide;
N-ethyl o-mercaptobenzamide; N-phenyl o-mercaptobenzamide;
N-cyclohexyl o-mercaptobenzamide; and N-norbornyl
o-mercaptobenzamide. S--O Valence Stabilizer #30: Examples of
S-alkylthiocarboxylic Acids, S-arylthiocarboxylic Acids, and
S,S-thiobiscarboxylic Acids (S--O Bidentates and S--O Tridentates)
that meet the requirements for use as "narrow band" valence
stabilizers for Co.sup.+3 include, but are not limited to:
(methylthio)acetic acid; (methylthio)benzoic acid;
(methylthio)nicotinic acid; (methylthio)napthoic acid;
(phenylthio)acetic acid; (phenylthio)benzoic acid;
(phenylthio)naphthoic acid; (norbornylthio)acetic acid;
(norbornylthio)benzoic acid; (norbornylthio)napthoic acid;
thiobisacetic acid; thiobisbenzoic acid; and thiobisnapthoic acid.
S--O Valence Stabilizer #31: Examples of S-alkyldisulfidocarboxylic
acids, S-aryldisulfidocarboxylic acids, and
S,S'-disulfidobiscarboxylic acids (S--O Bidentates and S--O
Tridentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
(methyldisulfido)acetic acid; (methyldisulfido)benzoic acid;
(methyldisulfido)nicotinic acid; (methyldisulfido)napthoic acid;
(phenyldisulfido)acetic acid; (phenyldisulfido)benzoic acid;
(phenyldisulfido)naphthoic acid; (norbornyldisulfido)acetic acid;
(norbornyldisulfido)benzoic acid; (norbornyldisulfido)napthoic
acid; S,S'-disulfidobisacetic acid; S,S'-disulfidobisbenzoic acid;
and S,S'-disulfidobisnapthoic acid. S--O Valence Stabilizer #32:
Examples ofmonothiomonocarboxylic acids, dithiodicarboxylic acids,
bis(monothiomonocarboxylic acids), bis(dithiodicarboxylic acids),
poly(monothiomonocarboxylic acids), poly(dithiodicarboxylic acids),
and derivatives thereof (S--O Bidentates and S--O Tetradentates)
that meet the requirements for use as "narrow band" valence
stabilizers for Co.sup.+3 include, but are not limited to:
thioacetic acid; thiopropionic acid; thiobenzoic acid;
thiophenylacetic acid; thiocyclohexanoic acid; thiofuroic acid;
thionaphthoic acid; phenyl thioacetate; phenyl thiopropionate;
phenyl thiobenzoate; phenyl thiocyclohexanoate; phenyl thiofuroate;
phenyl thionaphthoate; dithiooxalic acid (dto); monothiooxalic acid
(mtox); dithiomalonic acid; dithiosuccinic acid; diphenyl
dithiooxalate; diphenyl dithiomalonate; and diphenyl
dithiosuccinate. S--O Valence Stabilizer #33: Examples of
monothiocarbonates and bis(monothiocarbonates) (S--O Bidentates and
S--O Tetradentates) that meet the requirements for use as "narrow
band" valence stabilizers for Co.sup.+3 include, but are not
limited to: S,O-diethyldithiocarbonate;
S,O-diisopropyldithiocarbonate; S,O-diphenyldithiocarbonate;
S,O-dibenzyldithiocarbonate; S,O-dicyclohexyldithiocarbonate; and
S,O-dinorbornyldithiocarbonate. S--O Valence Stabilizer #34:
Examples of monothiocarbazates (monothiocarbazides),
bis(monothiocarbazates), and poly(monothiocarbazates) (S--O
Bidentates, S--O Tridentates, and S--O Tetradentates; or possibly
N--S Bidentates, N--S Tridentates, and N--S Tetradentates) that
meet the requirements for use as "narrow band" valence stabilizers
for Co.sup.+3 include, but are not limited to:
N,N'-dimethylmonothiocarbazate;
N,N'-di(trifluoromethyl)monothiocarbazate;
N,N'-diethylmonothiocarbazate; N,N'-diphenylmonothiocarbazate;
N,N'-dibenzylmonothiocarbazate;
N,N'-di(pentafluorophenyl)monothiocarbazate;
N,N'-dicyclohexylmonothiocarbazate; and
N,N'-dinorbornylmonothiocarbazate. S--O Valence Stabilizer #35:
Examples of mercapto alcohols and silylmercaptoalcohols,
bis(mercapto alcohols and silylmercaptoalcohols), and poly(mercapto
alcohols and silylmercaptoalcohols) (S--O Bidentates, S--O
Tridentates, S--O Tetradentates) that meet the requirements for use
as "narrow band" valence stabilizers for Co.sup.+3 include, but are
not limited to: 2-mercaptoethanol (mel); 3-mercaptopropanol (mpl);
2-mercaptophenol; 2-mercaptocyclohexanol; 3-mercapto-2-norborneol;
2-mercaptopyridine 1-oxide; 1,4-thioxane; thiodialkanols;
2-(trimethoxysilyl)-1-ethanethiol (tmset);
3-(trimethoxysilyl)-1-propanethiol (tmspt); o-hydroxythiophenols;
o-(O-hydroxyalkyl(aryl))thiophenols; and
o-(S-thioalkyl(aryl))phenols. S--O Valence Stabilizer #36: Examples
of monothiocarbimates, bis(monothiocarbimates), and
poly(monothiocarbimates) (S--O Bidentates, S--O Tridentates, and
S--O Tetradentates) that meet the requirements for use as "narrow
band" valence stabilizers for Co.sup.+3 include, but are not
limited to: methylmonothiocarbimate;
trifluoromethylmonothiocarbimate; ethylmonothiocarbimate;
propylmonothiocarbimate; isopropylmonothiocarbimate;
butylmonothiocarbimate; tertbutylmonothiocarbimate;
cyanomonothiocarbimate; cyanamidomonothiocarbimate;
azidomonothiocarbimate; phenylmonothiocarbimate;
pentafluorophenylmonothiocarbimate; benzylmonothiocarbimate;
naphthylmonothiocarbimate; cyclohexylmonothiocarbimate;
norbornylmonothiocarbimate; and adamantylmonothiocarbimate. [Note:
Carbimates tend to stabilize lower oxidation states in metal ions.]
S--O Valence Stabilizer #37: Examples of alkyl- and
aryl-monothioborates and bis(monothioborates) (S--O Bidentates and
S--O Tetradentates) that meet the requirements for use as "narrow
band" valence stabilizers for Co.sup.+3 include, but are not
limited to: O,O'-diethyl monothioborate; O,O'-diisopropyl
monothioborate; O,O'-diphenyl monothioborate; O,O'-dibenzyl
monothioborate; O,O'-dicyclohexyl monothioborate; and
O,O'-dinorbornyl monothioborate. S--O Valence Stabilizer #38:
Examples of alkyl- and aryl-monothioboronates and
bis(monothioboronates) (S--O Bidentates and S--O Tetradentates)
that meet the requirements for use as "narrow band" valence
stabilizers for Co.sup.+3 include, but are not limited to: diethyl
monothioboronate; diisopropyl monothioboronate; diphenyl
monothioboronate; dibenzyl monothioboronate; dicyclohexyl
monothioboronate; and dinorbornyl monothioboronate. [Note:
boronates tend to stabilize lower oxidation states in metal ions.]
S--O Valence Stabilizer #39: Examples of monothioarsonic acids
(arsonothioic acids), bis(monothioarsonic acids),
poly(monothioarsonic acids), and derivatives thereof(S--O
Bidentates, S--O Tridentates, S--O Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: monothioarsonic acid,
O-phenylmonothioarsonic acid, O-benzylmonothioarsonic acid,
O-cyclohexylmonothioarsonic acid, O-norbornylmonothioarsonic acid,
O,O-diphenylmonothioarsonic acid, O,O-dibenzylmonothioarsonic acid,
O,O-dicyclohexylmonothioarsonic acid, and
O,O-dinorbornylmonothioarsonic acid. S--O Valence Stabilizer #40:
Examples of heterocyclic rings containing one or two sulfur atoms
and having at least one additional oxygen atom binding site not in
a ring (S--O Bidentates, S--O Tridentates, S--O Tetradentates, or
S--O Hexadentates) that meet the requirements for use as "narrow
band" valence stabilizers for Co.sup.+3 include, but are not
limited to: 2-thiopheneethanol (2-(2-thienyl)ethanol);
2-propionylthiophene (1-(2-thienyl)-1-propanone);
N,N'-thiobisphthalimide; 1,1'-thiocarbonyldi-2-pyridone;
2-thiopheneacetic acid; 2-thiophenecarboxaldehyde;
2-thiophenecarboxamide; 2-thiophenecarboxylic acid;
2,5-thiophenedicarboxaldehyde; 2,5-thiophenedicarboxylic acid;
2-thiophenemethanol; 2-thiophenone; thiotetronic acid; alkyl(aryl)
2-thienyl ketones; dithienyl ketone; 1,3-dithiane-2-carboxylic
acid; and 1,3-dithiolane-2-carboxylic acid. S--O Valence Stabilizer
#41: Examples of heterocyclic rings containing one or two oxygen
atoms and having at least one additional sulfur atom binding site
not in a ring (S--O Bidentates, S--O Tridentates, S--O
Tetradentates, or S--O Hexadentates) that meet the requirements for
use as "narrow band" valence stabilizers for Co.sup.+3 include, but
are not limited to: 2-furanethanethiol (2-(2-furyl)ethanethiol);
1-(2-furyl)-1-propanethione); 2-furanthioacetic acid;
2-furanthiocarboxaldehyde; 2-furanthiocarboxamide;
2-furanthiocarboxylic acid; 2,5-furandithiocarboxaldehyde;
2,5-furandithiocarboxylic acid; 2-furanmethanethiol; 2-furanthione;
furfuryl disulfide; furfuryl mercaptan; furfuryl sulfide; and
furfuryl methyl disulfide. S--O Valence Stabilizer #42: Examples of
heterocyclic rings containing one or two sulfur atoms and having at
least one additional oxygen atom binding site in a separate ring
(S--O Bidentates, S--O Tridentates, S--O Tetradentates, or S--O
Hexadentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
2-(2-furyl)thiophene; 2,5-(2-furyl)thiophene; 2-(2-furyl)thiopyran;
and 2,5-(2-furyl)thiopyran. S--O Valence Stabilizer #43: Examples
of two-, three-, four-, five-, six-, seven-, eight-, nine-, and
ten-membered macrocyclics, macrobicyclics, and macropolycyclics
(including catapinands, cryptands, cyclidenes, and sepulchrates)
wherein all binding sites are composed of sulfur (usually thiol,
mercapto, or thiocarbonyl groups) or oxygen (hydroxy, carboxy, or
carbonyl groups) and are not contained in component heterocyclic
rings (S--O Bidentates, S--O Tridentates, S--O Tetradentates, and
S--O Hexadentates) that meet the requirements for use as "narrow
band" valence stabilizers for Co.sup.+3 include, but are not
limited to: thiaoxacyclobutane ([4]aneOS); thiaoxacyclopentane
([5]aneOS); thiaoxacyclohexane ([6]aneOS); thiaoxacycloheptane
([7]aneOS); thiaoxacyclooctane ([8]aneOS); thiaoxacyclobutene
([4]eneOS); thiaoxacyclopentene ([5]eneOS); thiaoxacyclohexene
([6]eneOS); thiaoxacycloheptene ([7]eneOS); thiaoxacyclooctene
([8]eneOS); dithiaoxacyclohexane ([6]aneOS.sub.2);
dithiaoxacycloheptane ([7]aneOS.sub.2); dithiaoxacyclooctane
([8]aneOS.sub.2); dithiaoxacyclononane ([9]aneOS.sub.2);
dithiaoxacyclodecane ([10]aneOS.sub.2); dithiaoxacycloundecane
([11]aneOS.sub.2); dithiaoxacyclododecane ([12]aneOS.sub.2);
dithiaoxacyclohexene ([6]eneOS.sub.2); dithiaoxacycloheptene
([7]eneOS.sub.2); dithiaoxacyclooctene ([8]eneOS.sub.2);
dithiaoxacyclononene ([9]eneOS.sub.2); dithiaoxacyclodecene
([10]eneOS.sub.2); dithiaoxacycloundecene ([11]eneOS.sub.2);
dithiaoxacyclododecene ([12]eneOS.sub.2); dithiadioxacyclooctane
([8]aneO.sub.2S.sub.2); dithiadioxacyclononane
([9]aneO.sub.2S.sub.2); dithiadioxacyclodecane
([10]aneO.sub.2S.sub.2); dithiadioxacycloundecane
([11]aneO.sub.2S.sub.2); dithiadioxacyclododecane
([12]aneO.sub.2S.sub.2); dithiadioxacyclotridecane
([13]aneO.sub.2S.sub.2); dithiadioxacyclotetradecane
([14]aneO.sub.2S.sub.2); dithiadioxacyclopentadecane
([15]aneO.sub.2S.sub.2); dithiadioxacyclohexadecane
([16]aneO.sub.2S.sub.2); dithiadioxacycloheptadecane
([17]aneO.sub.2S.sub.2); dithiadioxacyclooctadecane
([18]aneO.sub.2S.sub.2); dithiadioxacyclononadecane
([19]aneO.sub.2S.sub.2); dithiadioxacycloeicosane
([20]aneO.sub.2S.sub.2); dithiadioxacyclooctadiene
([8]dieneo.sub.2S.sub.2); dithiadioxacyclononadiene
([9]dieneo.sub.2S.sub.2); dithiadioxacyclodecadiene
([10]dieneo.sub.2S.sub.2); dithiadioxacycloundecadiene
([11]dieneo.sub.2S.sub.2); dithiadioxacyclododecadiene
([12]dieneO.sub.2S.sub.2); dithiadioxacyclotridecadiene
([13]dieneo.sub.2S.sub.2); dithiadioxacyclotetradecadiene
([14]dieneO.sub.2S.sub.2); dithiadioxacyclopentadecadiene
([15]dieneO.sub.2S.sub.2); dithiadioxacyclohexadecadiene
([16]dieneO.sub.2S.sub.2); dithiadioxacycloheptadecadiene
([17]dieneo.sub.2S.sub.2); dithiadioxacyclooctadecadiene
([18]dieneo.sub.2S.sub.2); dithiadioxacyclononadecadiene
([19]dieneO.sub.2S.sub.2); and dithiadioxacycloeicosadiene
([20]dieneO.sub.2S.sub.2). S--O Valence Stabilizer #44: Examples of
four-, five-, six-, seven-, eight-, nine-, or ten-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
binding sites are composed of sulfur or oxygen and are contained in
component heterocyclic rings (S--O Tridentates, S--O Tetradentates,
or S--O Hexadentates) that meet the requirements for use as "narrow
band" valence stabilizers for Co.sup.+3 include, but are not
limited to: difurandithiophenes; difurantrithiophenes;
trifurantrithiophenes; and tetrafurantetrathiophenes. S--O Valence
Stabilizer #45: Examples of four-, five-, six-, seven-, eight-,
nine-, or ten-membered macrocyclics, macrobicyclics, and
macropolycyclics (including catapinands, cryptands, cyclidenes, and
sepulchrates) wherein all binding sites are composed of sulfur or
oxygen and are contained in a combination of heterocyclic rings and
thiol, mercapto, thiocarbonyl, hydroxy, carboxy, and carbonyl
groups (S--O Tridentates, S--O Tetradentates, or S--O Hexadentates)
that meet the requirements for use as "narrow band" valence
stabilizers for Co.sup.+3 include, but are not limited to:
dithiadifurandithiophenes; tetrathiadifurandithiophenes;
trithiatrifurantrithiophenes; trithiatrifurantrithiophenes;
tetrathiatetrafurantetrathiophenes; and
octathiatetrafurantetrathiophenes. S--O Valence Stabilizer #46:
Examples of sulfoxides that meet the requirements for use as
"narrow band" valence stabilizers for Co.sup.+3 include, but are
not limited to: dimethylsulfoxide (DMSO); diethylsulfoxide;
diphenylsulfoxide; and tetrahydrothiophene oxide. S--O Valence
Stabilizer #47: Examples of sulfones that meet the requirements for
use as "narrow band" valence stabilizers for Co.sup.+3 include, but
are not limited to: dimethyl sulfone; diethyl sulfone; and diphenyl
sulfone. S--O Valence Stabilizer #48: Examples of sulfur dioxide
ligands that meet the requirements for use as "narrow band" valence
stabilizers for Co.sup.+3 include, but are not limited to: sulfur
dioxide (--SO.sub.2) ligands. [Note: Sulfur dioxide is a reducing
agent, and complexed metal ions therefore tend to prefer lower
oxidation states.] N--P Valence Stabilizer #1: Examples of
aminoaryl phosphines and iminoaryl phosphines (N--P Bidentates,
N--P Tridentates, and N--P Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to:
tri(2-aminophenyl)phosphine; tri(2-aminophenyl)phosphine oxide; and
tri(2-aminophenyl)phosphine sulfide. N--P Valence Stabilizer #2:
Examples of heterocyclic rings containing one, two, three, or four
nitrogen atoms and having at least one additional phosphorus atom
binding site not in a ring (N--P Bidentates, N--P Tridentates, N--P
Tetradentates, or N--P Hexadentates) that meet the requirements for
use as "narrow band" valence stabilizers for Co.sup.+3 include, but
are not limited to: tri(2-imidazolyl)phosphine;
tri(2-pyrrolyl)phosphine; tri(2-pyridyl)phosphine;
tri(2-imidazolyl)phosphine oxide; tri(2-pyrrolyl)phosphine oxide;
tri(2-pyridyl)phosphine oxide; tri(2-imidazolyl)phosphine sulfide;
tri(2-pyrrolyl)phosphine sulfide; and tri(2-pyridyl)phosphine
sulfide. N--P Valence Stabilizer #3: Examples of heterocyclic rings
containing one, two, or three phosphorus atoms and having at least
one additional nitrogen atom binding site not in a ring (N--P
Bidentates, N--P Tridentates, N--P Tetradentates, or N--P
Hexadentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
2-aminophosphole; 2,5-diaminophosphole; 2-(aminomethyl)phosphole;
2,5-di(aminomethyl)phosphole; 2-aminophosphorin;
2,6-diaminophosphorin; 2-(aminomethyl)phosphorin;
2,6-di(aminomethyl)phosphorin; triaminocyclotriphosphazenes; and
hexaminocyclotriphosphazenes. N--P Valence Stabilizer #4: Examples
of heterocyclic rings containing one, two, three, or four nitrogen
atoms and having at least one additional phosphorus atom binding
site in a separate ring (N--P Bidentates, N--P Tridentates, N--P
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
2-(2-pyrrolyl)phosphole; 2,5-di(2-pyrrolyl)phosphole;
2-(2-pyridyl)phosphorin; and 2,6-(2-pyridyl)phosphorin. N--P
Valence Stabilizer #5: Examples of two-, three-, four-, five-,
six-, seven-, eight-, nine-, and ten-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all binding sites
are composed of nitrogen (usually amine or imine groups) or
phosphorus and are not contained in component heterocyclic rings
(N--P Bidentates, N--P Tridentates, N--P Tetradentates, and N--P
Hexadentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
cyclobiphosphazenes; cyclotriphosphazenes; cyclotetraphosphazenes;
cyclopentaphosphazenes; cyclohexaphosphazenes;
diphosphatetraazacyclooctatetraenes; diphospha-s-triazines; and
phosphas-triazines. N--P Valence Stabilizer #6: Examples of four-,
five-, six-, seven-, eight-, nine-, or ten-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all binding sites
are composed of nitrogen or phosphorus and are contained in
component heterocyclic rings (N--P Bidentates, N--P Tridentates,
N--P Tetradentates, or N--P Hexadentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: diphospholedipyrroles;
diphosphorindipyridines; triphospholetripyrrol es;
triphosphorintripyridines; tetraphospholetetrapyrroles; and
tetraphosphorintetrapyridines. N--P Valence Stabilizer #7: Examples
of four-, five-, six-, seven-, eight-, nine-, or ten-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
binding sites are composed of nitrogen or phosphorus and are
contained in a combination of heterocyclic rings and amine, imine,
and phosphine groups (N--P Bidentates, N--P Tridentates, N--P
Tetradentates, or N--P Hexadentates) that meet the requirements for
use as "narrow band" valence stabilizers for Co.sup.+3 include, but
are not limited to: azaphosphatetraphyrins;
diazadiphosphatetraphyrins; azaphosphahexaphyrins;
diazadiphosphahexaphyrins; triazatriphosphahexaphyrins; and
apholate. S--P Valence Stabilizer #1: Examples of thioaryl
phosphines (S--P Bidentates, S--P Tridentates, S--P Tetradentates,
and S--P Hexadentates) that meet the requirements for use as
"narrow band" valence stabilizers for Co.sup.+3 include, but are
not limited to: tri(2-mercaptophenyl)phosphine;
tri(2-mercaptophenyl)phosphine oxide; and
tri(2-mercaptophenyl)phosphine sulfide. S--P Valence Stabilizer #2:
Examples of heterocyclic rings containing one or two sulfur atoms
and having at least one additional phosphorus atom binding site not
in a ring (S--P Bidentates, S--P Tridentates, S--P Tetradentates,
or S--P Hexadentates) that meet the requirements for use as "narrow
band" valence stabilizers for Co.sup.+3 include, but are not
limited to: tri(2-thiophene)phosphine; tri(2-thiopyran)phosphine;
tri(2-thiophene)phosphine oxide; tri(2-thiopyran)phosphine oxide;
tri(2-thiophene)phosphine sulfide; and tri(2-thiopyran)phosphine
sulfide. S--P Valence Stabilizer #3: Examples of heterocyclic rings
containing one, two, orthree phosphorus atoms and having at least
one additional sulfur atom binding site not in a ring (S--P
Bidentates, S--P Tridentates, S--P Tetradentates, or S--P
Hexadentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
2-mercaptophosphole; 2,5-dimercaptophosphole;
2-(mercaptomethyl)phosphole; 2,5-di(mercaptomethyl)phosphole;
2-mercaptophosphorin; 2,6-dimercaptophosphorin;
2-(mercaptomethyl)phosphorin; and 2,6-di(mercaptomethyl)phosphorin.
S--P Valence Stabilizer #4: Examples of heterocyclic rings
containing one or two sulfur atoms and having at least one
additional phosphorus atom binding site in a separate ring (S--P
Bidentates, S--P Tridentates, S--P Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: 2-(2-thienyl)phosphole;
2,5-di(2-thienyl)phosphole; 2-(2-thienyl)phosphorin; and
2,6-(2-thienyl)phosphorin. S--P Valence Stabilizer #5: Examples of
two-, three-, four-, five-, six-, seven-, eight-, nine-, and
ten-membered macrocyclics, macrobicyclics, and macropolycyclics
(including catapinands, cryptands, cyclidenes, and sepulchrates)
wherein all binding sites are composed of sulfur (usually thiol,
mercapto, or thiocarbonyl groups) or phosphorus and are not
contained in component heterocyclic rings (S--P Bidentates, S--P
Tridentates, S--P Tetradentates, and S--P Hexadentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: phosphathiacyclobutane
([4]aneP S); phosphathiacyclopentane ([5]aneP S);
phosphathiacyclohexane ([6]anePS); phosphathiacycloheptane
([7]anePS); phosphathiacyclooctane ([8]anePS);
diphosphathiacyclohexane ([6]aneSP.sub.2);
diphosphathiacycloheptane ([7]aneSP.sub.2);
diphosphathiacyclooctane ([8]aneSP.sub.2); diphosphathiacyclononane
([9]aneSP.sub.2); diphosphathiacyclodecane ([10]aneSP.sub.2);
diphosphathiacycloundecane ([11]aneSP.sub.2);
diphosphathiacyclododecane ([12]aneSP.sub.2);
diphosphadithiacyclooctane ([8]aneS.sub.2P.sub.2);
diphosphadithiacyclononane ([9]aneS.sub.2P.sub.2);
diphosphadithiacyclodecane ([10]aneS.sub.2P.sub.2);
diphosphadithiacycloundecane ([11]aneS.sub.2P.sub.2);
diphosphadithiacyclododecane ([12]aneS.sub.2P.sub.2);
diphosphadithiacyclotridecane ([13]aneS.sub.2P.sub.2);
diphosphadithiacyclotetradecane ([14]aneS.sub.2P.sub.2);
diphosphadithiacyclopentadecane ([15]aneS.sub.2P.sub.2);
diphosphadithiacyclohexadecane ([16]aneS.sub.2P.sub.2);
diphosphadithiacycloheptadecane ([17]aneS.sub.2P.sub.2);
diphosphadithiacyclooctadecane ([18]aneS.sub.2P.sub.2);
diphosphadithiacyclononadecane ([19]aneS.sub.2P.sub.2);
diphosphadithiacycloeicosane ([20]aneS.sub.2P.sub.2). S--P Valence
Stabilizer #6: Examples of four-, five-, six-, seven-, eight-,
nine-, or ten-membered macrocyclics, macrobicyclics, and
macropolycyclics (including catapinands, cryptands, cyclidenes, and
sepulchrates) wherein all binding sites are composed of sulfur or
phosphorus and are contained in component heterocyclic rings (S--P
Bidentates, S--P Tridentates, S--P Tetradentates, or S--P
Hexadentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
diphospholedithiophenes; diphosphorindithiopyrans;
triphospholetrithiophenes; triphosphorintrithiopyrans;
tetraphospholetetrathiophenes; and tetraphosphorintetrathiopyrans.
S--P Valence Stabilizer #7: Examples of four-, five-, six-, seven-,
eight-, nine-, or ten-membered macrocyclics, macrobicyclics, and
macropolycyclics (including catapinands, cryptands, cyclidenes, and
sepulchrates) wherein all binding sites are composed of sulfur or
phosphorus and are contained in a combination of heterocyclic rings
and thiol, mercapto, thiocarbonyl, and phosphine groups (S--P
Bidentates, S--P Tridentates, S--P Tetradentates, or S--P
Hexadentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
thiaphosphatetraphyrins; dithiadiphosphatetraphyrins;
thiaphosphahexaphyrins; dithiadiphosphahexaphyrins; and
trithiatriphosphahexaphyrins. P--O Valence Stabilizer #1: Examples
ofhydroxyaryl phosphines (P--O Bidentates, P--O Tridentates, P--O
Tetradentates, and P--O Hexadentates) that meet the requirements
for use as "narrow band" valence stabilizers for Co.sup.+3 include,
but are not limited to: tri(2-hydroxyphenyl)phosphine;
tri(2-hydroxyphenyl)phosphine oxide; and
tri(2-hydroxyphenyl)phosphine sulfide. P--O Valence Stabilizer #2:
Examples ofheterocyclic rings containing one or two oxygen atoms
and having at least one additional phosphorus atom binding site not
in a ring (P--O Bidentates, P--O Tridentates, P--O Tetradentates,
or P--O Hexadentates) that meet the requirements for use as "narrow
band" valence stabilizers for Co.sup.+3 include, but are not
limited to: tri(2-furan)phosphine; tri(2-pyran)phosphine;
tri(2-furan)phosphine oxide; tri(2-pyran)phosphine oxide;
tri(2-furan)phosphine sulfide; and tri(2-pyran)phosphine sulfide.
P--O Valence Stabilizer #3: Examples of heterocyclic rings
containing one, two, or three phosphorus atoms and having at least
one additional oxygen atom binding site not in a ring (P--O
Bidentates, P--O Tridentates, P--O Tetradentates, or P--O
Hexadentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
2-hydroxyphosphole; 2,5-dihydroxyphosphole;
2-(hydroxymethyl)phosphole; 2,5-di(hydroxymethyl)phosphole;
2-hydroxyphosphorin; 2,6-dihydroxyphosphorin;
2-(hydroxymethyl)phosphorin; and 2,6-di(hydroxymethyl)phosphorin.
P--O Valence Stabilizer #4: Examples of heterocyclic rings
containing one or two oxygen atoms and having at least one
additional phosphorus atom binding site in a separate ring (P--O
Bidentates, P--O Tridentates, P--O Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: 2-(2-furyl)phosphole;
2,5-di(2-furyl)phosphole; 2-(2-furyl)phosphorin; and
2,6-(2-furyl)phosphorin. P--O Valence Stabilizer #5: Examples of
two-, three-, four-, five-, six-, seven-, eight-, nine-, and
ten-membered macrocyclics, macrobicyclics, and macropolycyclics
(including catapinands, cryptands, cyclidenes, and sepulchrates)
wherein all binding sites are composed of oxygen (usually hydroxy,
carboxy, or carbonyl groups) or phosphorus and are not contained in
component heterocyclic rings (P--O Bidentates, P--O Tridentates,
P--O Tetradentates, and P--O Hex adentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: phosphaoxacyclobutane
([4]anePO); phosphaoxacyclopentane ([5]anePO);
phosphaoxacyclohexane ([6]anePO); phosphaoxacycloheptane
([7]anePO); phosphaoxacyclooctane ([8]anePO);
diphosphaoxacyclohexane ([6]aneOP.sub.2); diphosphaoxacycloheptane
([7]aneOP.sub.2); diphosphaoxacyclooctane ([8]aneOP.sub.2);
diphosphaoxacyclononane ([9]aneOP.sub.2); diphosphaoxacyclodecane
([10]aneOP.sub.2); diphosphaoxacycloundecane ([11]aneOP.sub.2);
diphosphaoxacyclododecane ([12]aneOP.sub.2);
diphosphadioxacyclooctane ([8]aneO.sub.2P.sub.2);
diphosphadioxacyclononane ([9]aneO.sub.2P.sub.2);
diphosphadioxacyclodecane ([10]aneO.sub.2P.sub.2);
diphosphadioxacycloundecane ([11]aneO.sub.2P.sub.2);
diphosphadioxacyclododecane ([12]aneO.sub.2P.sub.2);
diphosphadioxacyclotridecane ([13]aneO.sub.2P.sub.2);
diphosphadioxacyclotetradecane ([14]aneO.sub.2P.sub.2);
diphosphadioxacyclopentadecane ([15]aneO.sub.2P.sub.2);
diphosphadioxacyclohexadecane ([16]aneO.sub.2P.sub.2);
diphosphadioxacycloheptadecane ([17]aneO.sub.2P.sub.2);
diphosphadioxacyclooctadecane ([18]aneO.sub.2P.sub.2);
diphosphadioxacyclononadecane ([19]aneO.sub.2P.sub.2);
diphosphadioxacycloeicosane ([20]aneO.sub.2P.sub.2); and
dioxaphospholane. P--O Valence Stabilizer #6: Examples of four-,
five-, six-, seven-, eight-, nine-, or ten-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all binding sites
are composed of oxygen or phosphorus and are contained in component
heterocyclic rings (P--O Bidentates, P--O Tridentates, P--O
Tetradentates, or P--O Hexadentates) that meet the requirements for
use as "narrow band" valence stabilizers for Co.sup.+3 include, but
are not limited to: diphospholedifurans; diphosphorindipyrans;
triphospholetrifurans; triphosphorintripyrans;
tetraphospholetetrafurans; and tetraphosphorintetrapyrans. P--O
Valence Stabilizer #7: Examples of four-, five-, six-, seven-,
eight-, nine-, or ten-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all binding sites
are composed of oxygen or phosphorus and are contained in a
combination of heterocyclic rings and hydroxy, carboxy, carbonyl,
and phosphine groups (P--O Bidentates, P--O Tridentates, P--O
Tetradentates, or P--O Hexadentates) that meet the requirements for
use as "narrow band" valence stabilizers for Co.sup.+3 include, but
are not limited to: oxaphosphatetraphyrins;
dioxadiphosphatetraphyrins; oxaphosphahexaphyrins;
dioxadiphosphahexaphyrins; and trioxatriphosphahexaphyrins. As
Valence Stabilizer #1: Examples ofmonoarsines (As Monodentates)
that meet the requirements for use as "narrow band" valence
stabilizers for Co.sup.+3 include, but are not limited to: arsine,
triphenylarsine, ticyclohexylarsine, methyldiphenylarsine,
ethyldiphenylarsine, arsinonorbornane, and arsinoadamantane. As
Valence Stabilizer #2: Examples of diarsines (As Monodentates or
As--As Bidentates) that meet the requirements for use as "narrow
band" valence stabilizers for Co.sup.+3 include, but are not
limited to: bis(diphenylarsino)methane, bis(diphenylarsino)ethane,
bis(diphenylarsino)propane, bis(diphenylarsino)butane,
bis(diphenylarsino)pentane, 1,2-diarsinobenzene,
cyclohexane-1,2-diarsine, 1,2-bis(phenylbutylarsino)ethane,
o-phenylenebis(methylphenylarsine) and
o-phenylenebis(dimethylarsine) (diars). (Note: the aryl derivatives
are air-stable, whereas the alkyl derivatives are air-sensitive and
therefore unsuitable for these applications.) As Valence Stabilizer
#3: Examples of triarsines (As--As Bidentates, or As--As
Tridentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
1,1,5,9,9-pentaphenyl-1,5,9-triarsanonane,
3-methyl-3-(As,As-dimethyl)arsinomethyl-1,1,5,5-tetraphenyl-1,5-diarsapen-
tane, As,As-[o-(As-dimethyl)arsinodiphenyl]-(As-phenyl)arsine,
As,As-[o-(As-diphenyl)arsinodiphenyl]-(As-phenyl)arsine,
hexahydro-2,4,6-trimethyl-1,3,5-triarsinazine. (Note: the aryl
derivatives are air-stable, whereas the alkyl derivatives are
air-sensitive and therefore unsuitable for these applications.) As
Valence Stabilizer #4: Examples oftetraarsines (As--As Bidentates,
As--As Tridentates, or As--As Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to:
3,3-(As-diphenyl)arsinomethyl-1,1,5,5-tetraphenyl-1,5-diarsapentane.
(Note: the aryl derivatives are air-stable, whereas the alkyl
derivatives are air-sensitive and therefore unsuitable for these
applications.) As Valence Stabilizer #5: Examples of pentaarsines
(As--As Bidentates, As--As Tridentates, or As--As Tetradentates)
that meet the requirements for use as "narrow band" valence
stabilizers for Co.sup.+3 include, but are not limited to:
4-[2-(As-diphenyl)arsinoethyl]-1,1,7,10,10-pentaphenyl-1,4,7,10-tetraarsa-
decane. (Note: the aryl derivatives are air-stable, whereas the
alkyl derivatives are air-sensitive and therefore unsuitable for
these applications.) As Valence Stabilizer #6: Examples of
hexaarsines (As--As Bidentates, As--As Tridentates, As--As
Tetradentates, or As--As Hexadentates) that meet the requirements
for use as "narrow band" valence stabilizers for Co.sup.+3 include,
but are not limited to:
o-phenylenebis[di-3-(As-diphenyl)arsinopropylarsine]. (Note: the
aryl derivatives are air-stable, whereas the alkyl derivatives are
air-sensitive and therefore unsuitable for these applications.) As
Valence Stabilizer #7: Examples of 5-membered heterocyclic rings
containing one arsenic atom (As Monodentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: arsole, azarsole,
diazarsole, benzarsole, benzazarsole, dibenzarsole, naphtharsole,
naphthazarsole. As Valence Stabilizer #8: Examples of 6-membered
heterocyclic rings containing one arsenic atom (As Monodentates)
that meet the requirements for use as "narrow band" valence
stabilizers for Co.sup.+3 include, but are not limited to: arsenin,
azarsenin, diazarsenin, benzarsenin, benzazarsenin, dibenzarsenin,
naphtharsenin, and naphthazarsenin. As Valence Stabilizer #9:
Examples of 5-membered heterocyclic rings containing one arsenic
atom and having at least one additional arsenic atom binding site
not contained in a ring (As Monodentates, As--As Bidentates, As--As
Tridentates, As--As Tetradentates, or As--As Hexadentates) that
meet the requirements for use as "narrow band" valence stabilizers
for Co.sup.+3 include, but are not limited to:
2-(As-phenylarsino)arsole; 2,5-(As-phenylarsino)arsole;
2-(As-phenylarsino)benzarsole; 7-(As-phenylarsino)benzarsole; and
1,8-(As-phenylarsino)dibenzarsole. As Valence Stabilizer #10:
Examples of 6-membered heterocyclic rings containing one arsenic
atom and having at least one additional arsenic atom binding site
not contained in a ring (As Monodentates, As--As Bidentates, As--As
Tridentates, As--As Tetradentates, or As--As Hexadentates) that
meet the requirements for use as "narrow band" valence stabilizers
for Co.sup.+3 include, but are not limited to:
2-(As-phenylarsino)arsenin; 2,5-(As-phenylarsino)arsenin;
2-(As-phenylarsino)benzarsenin; 7-(As-phenylarsino)benzarsenin; and
1,9-(As-phenylarsino)dibenzarsenin. As Valence Stabilizer #11:
Examples of 5-membered heterocyclic rings containing one arsenic
atom and having at least one additional arsenic atom binding site
contained in a ring (As Monodentates, As--As Bidentates, As--As
Tridentates, As--As Tetradentates) that meet the requirements for
use as "narrow band" valence stabilizers for Co.sup.+3 include, but
are not limited to: 2,2'-biarsole; 2,2',2''-triarsole; and
2,2'-bibenzarsole. As Valence Stabilizer #12: Examples of
6-membered heterocyclic rings containing one arsenic atom and
having at least one additional arsenic atom binding site contained
in a ring (As Monodentates, As--As Bidentates, As--As Tridentates,
As--As Tetradentates) that meet the requirements for use as "narrow
band" valence stabilizers for Co.sup.+3 include, but are not
limited to: 2,2'-biarsenin; 2,2',2''-triarsenin;
2,2',2'',2'''-tetraarsenin; 2,2'-bibenzarsenin; and
8,8'-bibenzarsenin. As Valence Stabilizer #13a: Examples of
two-membered macrocyclics, macrobicyclics, and macropolycyclics
(including catapinands, cryptands, cyclidenes, and sepulchrates)
wherein both binding sites are composed of arsenic and are not
contained in component heterocyclic rings (As--As Bidentates) that
meet the requirements for use as "narrow band" valence stabilizers
for Co.sup.+3 include, but are not limited to:
As,As-diphenyldiarsacyclobutane ([4]aneAs2);
As,As-diphenyldiarsacyclopentane ([5]aneAs.sub.2);
As,As-diphenyldiarsacyclohexane ([6]aneAs2);
As,As-diphenyldiarsacycloheptane ([7]aneAs.sub.2);
As,As-diphenyldiarsacyclooctane ([8]aneAs2);
As,As-diphenyldiarsacyclobutene ([4]eneAs.sub.2);
As,As-diphenyldiarsacyclopentene ([5]eneAs2);
As,As-diphenyldiarsacyclohexene ([6]eneAs.sub.2);
As,As-diphenyldiarsacycloheptene ([7]eneAs2); and
As,As-diphenyldiarsacyclooctene ([8]eneAs.sub.2). As Valence
Stabilizer #13b: Examples of three-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all binding sites
are composed of arsenic and are not contained in component
heterocyclic rings (As--As Tridentates) that meet the requirements
for use as "narrow band" valence stabilizers for Co.sup.+3 include,
but are not limited to: As,As,As-triphenyltriarsacyclohexane
([6]aneAs.sub.3); As,As,As-triphenyltriarsacycloheptane
([7]aneAs.sub.3); As,As,As-triphenyltriarsacyclooctane
([8]aneAs.sub.3); As,As,As-triphenyltriarsacyclononane
([9]aneAs.sub.3); As,As,As-triphenyltriarsacyclodecane
([10]aneAs.sub.3); As,As,As-triphenyltriarsacycloundecane
([11]aneAs.sub.3); As,As,As-triphenyltriarsacyclododecane
([12]aneAs.sub.3); As,As,As-triphenyltriarsacyclohexatriene
([6]trieneAs.sub.3); As,As,As-triphenyltriarsacycloheptatriene
([7]trieneAs.sub.3); As,As,As-triphenyltriarsacyclooctatriene
([8]trieneAs.sub.3); As,As,As-triphenyltriarsacyclononatriene
([9]trieneAs.sub.3); As,As,As-triphenyltriarsacyclodecatriene
([10]trieneAs.sub.3); As,As,As-triphenyltriarsacycloundecatriene
([11]trieneAs.sub.3); and
As,As,As-triphenyltriarsacyclododecatriene ([12]trieneAs.sub.3). As
Valence Stabilizer #13c: Examples of four-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all binding sites
are composed of arsenic and are not contained in component
heterocyclic rings (As--As Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to:
As,As,As,As-tetraphenyltetraarsacyclooctane ([8]aneAs.sub.4);
As,As,As,As-tetraphenyltetraarsacyclononane ([9]aneAs.sub.4);
As,As,As,As-tetraphenyltetraarsacyclodecane ([10]aneAs.sub.4);
As,As,As,As-tetraphenyltetraarsacycloundecane ([11]aneAs.sub.4);
As,As,As,As-tetraphenyltetraarsacyclododecane ([12]aneAs.sub.4);
As,As,As,As-tetraphenyltetraarsacyclotridecane ([13]aneAs.sub.4);
As,As,As,As-tetraphenyltetraarsacyclotetradecane ([14]aneAs.sub.4);
As,As,As,As-tetraphenyltetraarsacyclopentadecane ([15]aneAs.sub.4);
As,As,As,As-tetraphenyltetraarsacyclohexadecane ([16]aneAs.sub.4);
As,As,As,As,As-tetraphenyltetraarsacycloheptadecane
([17]aneAs.sub.4); As,As,As,As-tetraphenyltetraarsacyclooctadecane
([18]aneAs.sub.4); As,As,As,As-tetraphenyltetraarsacyclononadecane
([19]aneAs.sub.4); and
As,As,As,As-tetraphenyltetraarsacycloeicosane ([20]aneAs.sub.4). As
Valence Stabilizer #13d: Examples of six-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all binding sites
are composed of arsenic and are not contained in component
heterocyclic rings (As--As Tridentates, As--As Tetradentates, or
As--As Hexadentates) that meet the requirements for use as "narrow
band" valence stabilizers for Co.sup.+3 include, but are not
limited to: As,As,As,As,As,As-hexaphenylhexaarsacyclododecane
([12]aneAs.sub.6);
As--As,As,As,As,As-hexaphenylhexaarsacyclotridecane
([13]aneAs.sub.6);
As,As,As,As,As,As-hexaphenylhexaarsacyclotetradecane
([14]aneAs.sub.6);
As,As,As,As,As,As-hexaphenylhexaarsacyclopentadecane
([15]aneAs.sub.6);
As,As,As,As,As,As-hexaphenylhexaarsacyclohexadecane
([16]aneAs.sub.6);
As,As,As,As,As,As-hexaphenylhexaarsacycloheptadecane
([17]aneAs.sub.6);
As,As,As,As,As,As-hexaphenylhexaarsacyclooctadecane
([18]aneAs.sub.6);
As,As,As,As,As,As-hexaphenylhexaarsacyclononadecane
([19]aneAs.sub.6);
As,As,As,As,As,As-hexaphenylhexaarsacycloeicosane
([20]aneAs.sub.6);
As,As,As,As,As,As-hexaphenylhexaarsacycloheneicosane
([21]aneAs.sub.6);
As,As,As,As,As,As-hexaphenylhexaarsacyclodocosane
([22]aneAs.sub.6);
As,As,As,As,As,As-hexaphenylhexaarsacyclotricosane
([23]aneAs.sub.6); and
As,As,As,As,As,As-hexaphenylhexaarsacyclotetracosane
([24]aneAs.sub.6). As Valence Stabilizer #14a: Examples of
four-membered macrocyclics, macrobicyclics, and macropolycyclics
(including catapinands, cryptands, cyclidenes, and sepulchrates)
wherein all four binding sites are composed of arsenic and are
contained in component 5-membered heterocyclic rings (As--As
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
tetraarsoles. As Valence Stabilizer #14b: Examples of six-membered
macrocyclics, macrobicyclics, and macropolycyclics (including
catapinands, cryptands, cyclidenes, and sepulchrates) wherein all
six binding sites are composed of arsenic and are contained in
component 5-membered heterocyclic rings (As--As Tetradentates and
As--As Hexadentates) that meet the requirements for use as "narrow
band" valence stabilizers for Co.sup.+3 include, but are not
limited to: hexaarsoles. As Valence Stabilizer #15a: Examples of
four-membered macrocyclics, macrobicyclics, and macropolycyclics
(including catapinands, cryptands, cyclidenes, and sepulchrates)
wherein all four binding sites are composed of arsenic and are
contained in a combination of 5-membered heterocyclic rings and
arsine groups (As--As Tridentates, As--As Tetradentates) that meet
the requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: diarsatetraarsoles; and
tetraarsatetraarsoles. As Valence Stabilizer #15b: Examples of
six-membered macrocyclics, macrobicyclics, and macropolycyclics
(including catapinands, cryptands, cyclidenes, and sepulchrates)
wherein all six binding sites are composed of arsenic and are
contained in a combination of 5-membered heterocyclic rings and
phosphine groups (As--As Tridentates, As--As Tetradentates, and
As--As Hexadentates) that meet the requirements for use as "narrow
band" valence stabilizers for Co.sup.+3 include, but are not
limited to: diarsahexaarsoles; and triarsahexaarsoles. As Valence
Stabilizer #16a: Examples of four-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all four binding
sites are composed of arsenic and are contained in component
6-membered heterocyclic rings (As--As Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: cyclotetraarsenins. As
Valence Stabilizer #16b: Examples of six-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all six binding
sites are composed of arsenic and are contained in component
6-membered heterocyclic rings (As--As Tridentates, As--As
Tetradentates, and As--As Hexadentates) that meet the requirements
for use as "narrow band" valence stabilizers for Co.sup.+3 include,
but are not limited to: cyclohexaarsenins. As Valence Stabilizer
#17a: Examples of four-membered macrocyclics, macrobicyclics, and
macropolycyclics (including catapinands, cryptands, cyclidenes, and
sepulchrates) wherein all four binding sites are composed of
arsenic and are contained in a combination of 6-membered
heterocyclic rings and arsine groups (As--As Tridentates, As--As
Tetradentates, or As--As Hexadentates) that meet the requirements
for use as "narrow band" valence stabilizers for Co.sup.+3 include,
but are not limited to: diarsacyclotetraarsenins; and
tetraarsacyclotetraarsenins. As Valence Stabilizer #17b: Examples
of six-membered macrocyclics, macrobicyclics, and macropolycyclics
(including catapinands, cryptands, cyclidenes, and sepulchrates)
wherein all six binding sites are composed of arsenic and are
contained in a combination of 6-membered heterocyclic rings and
arsine groups (As--As Tridentates, As--As Tetradentates, or As--As
Hexadentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
diarsacyclohexaarsenins; and triarsacyclohexaarsenins. Se Valence
Stabilizer #1: Examples of monoselenoethers (Se Monodentates) that
meet the requirements for use as "narrow band" valence stabilizers
for Co.sup.+3 include, but are not limited to: hydrogen selenide,
dimethyl selenide, diethyl selenide, dioctyl selenide, diphenyl
selenide, dicyclohexyl selenide, tetramethylene selenide,
trimethylene selenide, dimethylene selenide, and
selenobicycloheptane. Se Valence Stabilizer #2: Examples of
diselenoethers (Se Bidentates) that meet the requirements for use
as "narrow band" valence stabilizers for Co.sup.+3 include, but are
not limited to: 2,5-dimethyl-3,6-diselenaoctane;
2,5-diselenahexane; 2,6-diselenaheptane; 3,7-diselenanonane;
3,6-diselenaoctane; 3-butenyl butyl selenoether (bbs); 4-pentenyl
butyl selenoether (pbs); 3-butenyl phenyl selenoether (bps); and
4-pentenyl phenyl selenoether (pps). Se Valence Stabilizer #3:
Examples of triselenoethers (Se Bidentates or Se Tridentates) that
meet the requirements for use as "narrow band" valence stabilizers
for Co.sup.+3 include, but are not limited to: 1,3,5-triselenane;
2,5,8-triselenanonane; 3,6,9-triselenaundecane; and
2,6,10-triselenaundecane. Se Valence Stabilizer #4: Examples of
tetraselenoethers (Se Bidentates, Se Tridentates, or Se
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
2,6,10,14-tetraselenapentadecane and 2,5,8,11-tetraselenadodecane.
Se Valence Stabilizer #5a: Examples of 5-membered heterocyclic
rings containing one selenium atom (Se Monodentates) that meet the
requirements
for use as "narrow band" valence stabilizers for Co.sup.+3 include,
but are not limited to: dihydroselenophene, selenophene,
selenazole, selenapyrroline, selenaphospholene, selenaphosphole,
oxaselenole, selenadiazole, selenatriazole,
benzodihydroselenophene, benzoselenophene, benzoselenazole,
benzoselenaphosphole, dibenzoselenophene, and naphthoselenophene.
Se Valence Stabilizer #5b: Examples of 5-membered heterocyclic
rings containing two selenium atoms (Se Monodentates or Se
Bidentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
diselenole, benzodiselenole, and naphthodiselenole. Se Valence
Stabilizer #6a: Examples of 6-membered heterocyclic rings
containing one selenium atom (Se Monodentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: dihydroselenopyran,
selenopyran, selenazine, selenadiazine, selenaphosphorin,
selenadiphosphorin, oxaselenin, benzoselenopyran,
dibenzoselenopyran, and naphthoselenopyran. Se Valence Stabilizer
#6b: Examples of 6-membered heterocyclic rings containing two
selenium atoms (Se Monodentates or Se Bidentates)that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: dihydrodiselenin,
diselenin, benzodiselenin, dibenzodiselenin, and naphthodiselenin.
Se Valence Stabilizer #7: Examples of 5-membered heterocyclic rings
containing one selenium atom and having at least one additional
selenium atom binding site not contained in a ring (Se
Monodentates, Se--Se Bidentates, Se--Se Tridentates, Se--Se
Tetradentates, or Se--Se Hexadentates) that meet the requirements
for use as "narrow band" valence stabilizers for Co.sup.+3 include,
but are not limited to: 2,5-diseleno-2,5-dihydroselenophene;
2,5-bis(selenomethyl)-2,5-dihydroselenophene;
2,5-bis(2-selenophenyl)-2,5-dihydroselenophene;
2,5-diseleno(selenophene); 2,5-bis(selenomethyl)selenophene;
2,5-bis(2-selenophenyl)selenophene; 2,5-diseleno(selenazole);
2,5-bis(selenomethyl)selenazole; 2,5-bis(2-selenophenyl)selenazole;
and 2,5-diseleno-1,3,4-selenadiazole [bismuthselenol]. Se Valence
Stabilizer #8: Examples of 6-membered heterocyclic rings containing
one selenium atom and having at least one additional selenium atom
binding site not contained in a ring (Se Monodentates, Se--Se
Bidentates, Se--Se Tridentates, Se--Se Tetradentates, or Se--Se
Hexadentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
2,6-diseleno-2,5-dihydroselenopyran;
2,6-bis(selenomethyl)-2,5-dihydroselenopyran;
2,6-bis(2-selenophenyl)-2,5-dihydroselenopyran;
2,6-diseleno(selenopyran); 2,6-bis(selenomethyl)selenopyran;
2,6-bis(2-selenophenyl)selenopyran; 2,6-diseleno(selenazine);
2,6-bis(selenomethyl)selenazine; 2,6-bis(2-selenophenyl)selenazine;
2,6-diseleno-1,3,5-selenadiazine; 2-seleno-1-benzoselenopyran;
8-seleno-1-benzoselenopyran; and 1,9-diselenodibenzoselenopyran. Se
Valence Stabilizer #9: Examples of 5-membered heterocyclic rings
containing one selenium atom and having at least one additional
selenium atom binding site contained in a ring (Se Monodentates,
Se--Se Bidentates, Se--Se Tridentates, Se--Se Tetradentates) that
meet the requirements for use as "narrow band" valence stabilizers
for Co.sup.+3 include, but are not limited to:
2,2'-bi-2,5-dihydroselenophene;
2,2',2''-tri-2,5-dihydroselenophene; 2,2'-biselenophene;
2,2',2''-triselenophene; 2,2'-biselenazole; 5,5'-biselenazole;
2,2'-bi-1,3,4-selenadiazole; 2,2'-biselenanaphthene;
2,2'-bibenzoselenazole; and 1,1'-bis(dibenzoselenophene). Se
Valence Stabilizer #10: Examples of 6-membered heterocyclic rings
containing one selenium atom and having at least one additional
selenium atom binding site contained in a ring (Se Monodentates,
Se--Se Bidentates, Se--Se Tridentates, Se--Se Tetradentates) that
meet the requirements for use as "narrow band" valence stabilizers
for Co.sup.+3 include, but are not limited to:
2,2'-bi-2,5-dihydroselenopyran;
2,2',2''-tri-2,5-dihydroselenopyran; 2,2'-biselenopyran;
2,2',2''-triselenopyran; 2,2'-bi-1,4-selenazine;
2,2'-bi-1,3,5-selenadiazine; 2,2'-bi-1-benzoselenopyran; and
1,1'-bis(dibenzoselenopyran). Se Valence Stabilizer #11a: Examples
of two-membered macrocyclics, macrobicyclics, and macropolycyclics
(including catapinands, cryptands, cyclidenes, and sepulchrates)
wherein both binding sites are composed of selenium (usually
selenol or selenoether groups) and are not contained in component
heterocyclic rings (Se--Se Bidentates) that meet the requirements
for use as "narrow band" valence stabilizers for Co.sup.+3 include,
but are not limited to: diselenacyclobutane ([4]aneSe.sub.2);
diselenacyclopentane ([5]aneSe.sub.2); diselenacyclohexane
([6]aneSe.sub.2); diselenacycloheptane ([7]aneSe.sub.2);
diselenacyclooctane ([8]aneSe.sub.2); diselenacyclobutene
([4]eneSe.sub.2); diselenacyclopentene ([5]eneSe.sub.2);
diselenacyclohexene ([6]eneSe.sub.2); diselenacycloheptene
([7]eneSe.sub.2); diselenacyclooctene ([8]eneSe.sub.2);
diselenacyclobutadiene ([4]dieneSe.sub.2); diselenacyclopentadiene
([5]dieneSe.sub.2); diselenacyclohexadiene ([6]dieneSe.sub.2);
diselenacycloheptadiene ([7]dieneSe.sub.2); and
diselenacyclooctadiene ([8]dieneSe.sub.2). Se Valence Stabilizer
#11b: Examples of three-membered macrocyclics, macrobicyclics, and
macropolycyclics (including catapinands, cryptands, cyclidenes, and
sepulchrates) wherein all binding sites are composed of selenium
(usually selenol or selenoether groups) and are not contained in
component heterocyclic rings (Se--Se Tridentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: triselenacyclohexane
([6]aneSe.sub.3); triselenacycloheptane ([7]aneSe.sub.3);
triselenacyclooctane ([8]aneSe.sub.3); triselenacyclononane
([9]aneSe.sub.3); triselenacyclodecane ([10]aneSe.sub.3);
triselenacycloundecane ([11]aneSe.sub.3); triselenacyclododecane
([12]aneSe.sub.3); triselenacyclohexene ([6]eneSe.sub.3);
triselenacycloheptene ([7]eneSe.sub.3); triselenacyclooctene
([8]eneSe.sub.3); triselenacyclononene ([9]eneSe.sub.3);
triselenacyclodecene ([10]eneSe.sub.3); triselenacycloundecene
([11]eneSe.sub.3); triselenacyclododecene ([12]eneSe.sub.3);
triselenacyclohexatriene ([6]trieneSe.sub.3);
triselenacycloheptatriene ([7]trieneSe.sub.3);
triselenacyclooctatriene ([8]trieneSe.sub.3);
triselenacyclononatriene ([9]trieneSe.sub.3);
triselenacyclodecatriene ([10]trieneSe.sub.3);
triselenacycloundecatriene ([11]trieneSe.sub.3); and
triselenacyclododecatriene ([12]trieneSe.sub.3). Se Valence
Stabilizer #11c: Examples of four-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all binding sites
are composed of selenium (usually sclenol or selenoether groups)
and are not contained in component heterocyclic rings (Se--Se
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
tetraselenacyclooctane ([8]aneSe.sub.4); tetraselenacyclononane
([9]aneSe.sub.4); tetraselenacyclodecane ([11]aneSe.sub.4);
tetraselenacycloundecane ([11]aneSe.sub.4);
tetraselenacyclododecane ([12]aneSe.sub.4);
tetraselenacyclotridecane ([13]aneSe.sub.4);
tetraselenacyclotetradecane ([14]aneSe.sub.4);
tetraselenacyclopentadecane ([15]aneSe.sub.4);
tetraselenacyclohexadecane ([16]aneSe.sub.4);
tetraselenacycloheptadecane ([17]aneSe.sub.4);
tetraselenacyclooctadecane ([18]aneSe.sub.4);
tetraselenacyclononadecane ([19]aneSe.sub.4);
tetraselenacycloeicosane ([20]aneSe.sub.4);
tetraselenacyclooctadiene ([8]dieneSe.sub.4);
tetraselenacyclononadiene ([9]dieneSe.sub.4);
tetraselenacyclodecadiene ([10]dieneSe.sub.4);
tetraselenacycloundecadiene ([11]dieneSe.sub.4);
tetraselenacyclododecadiene ([12]dieneSe.sub.4);
tetraselenacyclotridecadiene ([13]dieneSe.sub.4);
tetraselenacyclotetradecadiene ([14]dieneSe.sub.4);
tetraselenacyclopentadecadiene ([15]dieneSe.sub.4);
tetraselenacyclohexadecadiene ([16]dieneSe.sub.4);
tetraselenacycloheptadecadiene ([17]dieneSe.sub.4);
tetraselenacyclooctadecadiene ([18]dieneSe.sub.4);
tetraselenacyclononadecadiene ([19]dieneSe.sub.4);
tetraselenacycloeicosadiene ([20]dieneSe.sub.4);
tetraselenacyclooctatetradiene ([8]tetradieneSe.sub.4);
tetraselenacyclononatetradiene ([9]tetradieneSe.sub.4);
tetraselenacyclodecatetradiene ([10]tetradieneSe.sub.4); and
tetraselenacycloundecatetradiene ([11]tetradieneSe.sub.4). Se
Valence Stabilizer #11d: Examples of six-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all binding sites
are composed of selenium (usually selenol or selenoether groups)
and are not contained in component heterocyclic rings (Se--Se
Tridentates, Se--Se Tetradentates, or Se--Se Hexadentates) that
meet the requirements for use as "narrow band" valence stabilizers
for Co.sup.+3 include, but are not limited to:
hexaselenacyclododecane ([12]aneSe.sub.6); hexaselenacyclotridecane
([13]aneSe.sub.6); hexaselenacyclotetradecane ([14]aneSe.sub.6);
hexaselenacyclopentadecane ([15]aneSe.sub.6);
hexaselenacyclohexadecane ([16]aneSe.sub.6);
hexaselenacycloheptadecane ([17]aneSe.sub.6);
hexaselenacyclooctadecane ([18]aneSe.sub.6);
hexaselenacyclononadecane ([19]aneSe.sub.6);
hexaselenacycloeicosane ([20]aneSe.sub.6);
hexaselenacycloheneicosane ([21]aneSe.sub.6);
hexaselenacyclodocosane ([22]aneSe.sub.6); hexaselenacyclotricosane
([23]aneSe.sub.6); hexaselenacyclotetracosane ([24]aneSe.sub.6);
hexaselenacyclododecatriene ([12]trieneSe.sub.6);
hexaselenacyclotridecatriene ([13]trieneSe.sub.6);
hexaselenacyclotetradecatriene ([14]trieneSe.sub.6);
hexaselenacyclopentadecatriene ([15]trieneSe.sub.6);
hexaselenacyclohexadecatriene ([16]trieneSe.sub.6);
hexaselenacycloheptadecatriene ([17]trieneSe.sub.6); and
hexaselenacyclooctadecatriene ([18]trieneSe.sub.6). Se Valence
Stabilizer #12a: Examples of four-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all four binding
sites are composed of selenium and are contained in component
5-membered heterocyclic rings (Se--Se Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: tetraselenophenes;
tetraselenaphospholes; tetraoxaselenoles; and tetradiselenoles. Se
Valence Stabilizer #12b: Examples of six-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all six binding
sites are composed of selenium and are contained in component
5-membered heterocyclic rings (Se--Se Tridentates or Se--Se
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
hexaselenophenes; hexaselenaphospholes; hexaoxaselenoles; and
hexadiselenoles. Se Valence Stabilizer #13a: Examples of
four-membered macrocyclics, macrobicyclics, and macropolycyclics
(including catapinands, cryptands, cyclidenes, and sepulchrates)
wherein all four binding sites are composed of selenium and are
contained in a combination of 5-membered heterocyclic rings and
selenol and selenoether groups (Se--Se Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: di
selenatetraselenophenes; tetraselenatetraselenophenes;
diselenatetradiselenoles; and tetraselenatetradiselenoles. Se
Valence Stabilizer #13b: Examples of six-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all six binding
sites are composed of selenium and are contained in a combination
of 5-membered heterocyclic rings and selenol or selenoether groups
(Se--Se Tridentates or Se--Se Hexadentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to:
diselenahexaselenophenes; and triselenahexaselenophenes. Se Valence
Stabilizer #14a: Examples of four-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all four binding
sites are composed of selenium and are contained in component
6-membered heterocyclic rings (Se--Se Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: tetraselenopyrans;
tetraselenaphosphorins; tetraselenadiphosphorins; tetraoxaselenins;
and tetradiselenins. Se Valence Stabilizer #14b: Examples of
six-membered macrocyclics, macrobicyclics, and macropolycyclics
(including catapinands, cryptands, cyclidenes, and sepulchrates)
wherein all six binding sites are composed of selenium and are
contained in component 6-membered heterocyclic rings (Se--Se
Tridentates or Se--Se Hexadentates) that meet the requirements for
use as "narrow band" valence stabilizers for Co.sup.+3 include, but
are not limited to: hexaselenopyrans; hexaselenaphosphorins;
hexaselenadiphosphorins; hexaoxaselenins; and hexadiselenins. Se
Valence Stabilizer #15a: Examples of four-membered macrocyclics,
macrobicyclics, and macropolycyclics (including catapinands,
cryptands, cyclidenes, and sepulchrates) wherein all four binding
sites are composed of selenium and are contained in a combination
of 6-membered heterocyclic rings and selenol or selenoether groups
(Se--Se Tetradentates) that meet the requirements for use as
"narrow band" valence stabilizers for Co.sup.+3 include, but are
not limited to: diselenatetraselenopyrans;
tetraselenatetraselenopyrans; diselenatetraselenaphosphorins;
tetraselenatetraselenaphosphorins; diselenatetraoxaselenins;
tetraselenatetraoxaselenins; diselenatetradiselenins; and
tetraselenatetradiselenins. Se Valence Stabilizer #15b: Examples of
six-membered macrocyclics, macrobicyclics, and macropolycyclics
(including catapinands, cryptands, cyclidenes, and sepulchrates)
wherein all six binding sites are composed of selenium and are
contained in a combination of 6-membered heterocyclic rings and
selenol or selenoether groups (Se--Se Tridentates, Se--Se
Tetradentates, or Se--Se Hexadentates) that meet the requirements
for use as "narrow band" valence stabilizers for Co.sup.+3 include,
but are not limited to: diselenahexaselenopyrans;
triselenahexaselenopyrans; diselenahexaselenaphosphorins;
triselenahexaselenaphosphorins; diselenahexaoxaselenins;
triselenahexaoxaselenins; diselenahexadiselenins; and
triselenahexadiselenins. Se Valence Stabilizer #16: Examples of
1,3-diselenoketones (diseleno-beta-ketonates),
1,3,5-triselenoketones, bis(1,3-diselenoketones), and
poly(1,3-diselenoketones) (Se--Se Bidentates, Se--Se Tridentates,
Se--Se Tetradentates) that meet the requirements for use as "narrow
band" valence si abilizers for Co.sup.+3 include, but are not
limited to: hexafluoropentanediselenone;
1,3-diphenyl-1,3-propanediselenone; selenobenzoylselenopinacolone;
diselenocyclohexoylmethane; diphenylpentanetriselenoate;
tetramethylnonanetriselenoate; hexafluoroheptanetriselenoate;
trifluoroheptanetriselenoate; 1-(2-thienyl)-1,3-butanediselenone,
1-(2-naphthyl)-1,3-butanediselenone, and
trifluoroselenoacetylselenocamphor. Se Valence Stabilizer #17:
Examples of 1,1-diselenolates, bis(1,1-diselenolates), and
poly(1,1-diselenolates) (Se--Se Bidentates and Se--Se
Tetradentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
1,1-dicyano-2,2-ethylene diselenolate;
1,1-dicarboalkoxy-2,2-ethylene diselenolate;
1,1-di(trifluoromethyl)-2,2-ethylene diselenolate;
1,1-di(pentafluorophenyl)-2,2-ethylene diselenolate;
1-pentamethylene-2,2-ethylene diselenolate; and 1-nitroethylene
diselenolate. Se Valence Stabilizer #18: Examples of
diselenocarbamates, bis(diselenocarbamates), and
poly(diselenocarbamates) (including N-hydroxydiselenocarbamates and
N-mercaptodiselenocarbamates) (Se--Se Bidentates, Se--Se
Tridentates, and Se--Se Tetradentates) that meet the requirements
for use as "narrow band" valence stabilizers for Co.sup.+3 include,
but are not limited to: dimethyldiselenocarbamate;
di(trifluorodimethyl)diselenocarbamate; diethyldiselenocarbamate;
dipropyldiselenocarbamate; diisopropyldiselenocarbamate;
dibutyldiselenocarbamate; ditertbutyldiselenocarbamate;
dicyanamidodiselenocarbamate; azidoselenoformates;
diphenyldiselenocarbamate; di(pentafluorophenyl)diselenocarbamate;
dibenzyldiselenocarbamate; dinaphthyldiselenocarbamate;
dicyclohexyldiselenocarbamate; dinorbornyldiselenocarbamate;
diadamantyldiselenocarbamate; pyrrolidinodiselenocarbamate;
piperidinodiselenocarbamate; morpholinodiselenocarbamate;
thiamorpholinodiselenocarbamate; 3-pyrrolinodiselenocarbamate;
pyrrolodiselenocarbamate; oxazolodiselenocarbamate;
isoxazolodiselenocarbamate; thiazolodiselenocarbamate;
isothiazolodiselenocarbamate; indolodiselenocarbamate;
carbazolodiselenocarbamate; pyrazolinodiselenocarbamate;
imidazolinodiselenocarbamate; pyrazolodiselenocarbamate;
imidazolodiselenocarbamate; indazolodiselenocarbamate; and
triazolodiselenocarbamate. Se Valence Stabilizer #19: Examples of
triselenophosphoric acids (phosphorotriselenoic acids),
bis(triselenophosphoric acids), poly(triselenophosphoric acids),
and derivatives thereof (Se--Se Bidentates, Se--Se Tridentates,
Se--Se Tetradentates) that meet the requirements for use as "narrow
band" valence stabilizers for Co.sup.+3 include, but are not
limited to: triselenophosphoric acid, O-phenyltriselenophosphoric
acid, O-benzyltriselenophosphoric acid,
O-cyclohexyltriselenophosphoric acid,
O-norbornyltriselenophosphoric acid,
O,Se-diphenyltriselenophosphoric acid,
O,Se-dibenzyltriselenophosphoric acid,
O,Se-dicyclohexyltriselenophosphoric acid, and
O,Se-dinorbornyltriselenophosphoric acid. Se Valence Stabilizer
#20: Examples of diselenophosphoric acids (phosphorodiselenoic
acids), bis(diselenophosphoric acids), poly(diselenophosphoric
acids), and derivatives thereof (Se--Se Bidentates, Se--Se
Tridentates, Se--Se Tetradentates) that meet the requirements for
use as "narrow band" valence stabilizers for Co.sup.+3 include, but
are not limited to: diselenophosphoric acid,
O-phenyldiselenophosphoric acid, O-benzyldiselenophosphoric acid,
O-cyclohexyldiselenophosphoric acid, O-norbornyldiselenophosphoric
acid, O,O-diphenyldiselenophosphoric acid,
O,O-dibenzyldiselenophosphoric acid,
O,O-dicyclohexyldiselenophosphoric acid, and
O,O-dinorbornyldiselenophosphoric acid. Se Valence Stabilizer #21:
Examples of tetraselenophosphoric acids (phosphorotetraselenoic
acids), bis(tetraselenophosphoric acids),
poly(tetraselenophosphoric acids), and derivatives thereof (Se--Se
Bidentates, Se--Se Tridentates, Se--Se Tetradentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: tetraselenophosphoric
acid, Se-phenyltetraselenophosphoric acid,
Se-benzyltetraselenophosphoric acid,
Se-cyclohexyltetraselenophosphoric acid,
Se-norbornyltetraselenophosphoric acid,
Se,Se-diphenyltetraselenophosphoric acid,
Se,Se-dibenzyltetraselenophosphoric acid,
Se,Se-dicyclohexyltetraselenophosphoric acid, and
Se,Se-dinorbornyltetraselenophosphoric acid. Se Valence Stabilizer
#22: Examples of diselenocarbonates, triselenocarbonates,
bis(diselenocarbonates), and bis(triselenocarbonates), (Se--Se
Bidentates and S--S Tetradentates) that meet the requirements for
use as "narrow band" valence stabilizers for Co.sup.+3 include, but
are not limited to: Se,Se-diethyldiselenocarbonate;
Se,Se-diisopropyldiselenocarbonate; Se,Se-diphenyldisel
enocarbonate; Se,Se-dibenzyldi sel enocarbonate;
Se,Se-dicyclohexyldiselenocarbonate;
Se,Se-dinorbornyldiselenocarbonate; diethyltriselenocarbonate;
diisopropyltriselenocarbonate; diphenyltriselenocarbonate;
dibenzyltriselenocarbonate; dicyclohexyltriselenocarbonate; and
dinorbornyltriselenocarbonate. Se Valence Stabilizer #23: Examples
of selenocyanate ligands (Se monodentates) that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: selenocyanate (--SeCN).
Se Valence Stabilizer #24: Examples of selenolates (Se
monodentates) that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
selenophenol; and naphthaleneselenol. MiscellaneousValence
Stabilizer#1: Examples of diene,bicyclicand tricyclichydrocarbon
ligands that meet the requirements for use as "narrow band" valence
stabilizers for Co.sup.+3 include, but are not limited to:
cyclopentadiene; azulene; carotene; norbornane; and adamantane.
Miscellaneous Valence Stabilizer #2: Examples of cyanide and
related ligands that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
cyanide (--CN); and fulminate (--CNO). Miscellaneous Valence
Stabilizer #3: Examples of carbonyl ligands that meet the
requirements for use as "narrow band" valence stabilizers for
Co.sup.+3 include, but are not limited to: carbonyl (--CO); and
carbon dioxide (CO.sub.2) ligands. Miscellaneous Valence Stabilizer
#4: Examples of halogens that meet the requirements for use as
"narrow band" valence stabilizers for Co.sup.+3 include, but are
not limited to: fluorine; chlorine; bromine; and iodine.
Miscellaneous Valence Stabilizer #5: Examples of hydroxo and oxo
functionalities that meet the requirements for use as "narrow band"
valence stabilizers for Co.sup.+3 include, but are not limited to:
water (H.sub.2O); dioxygen (O.sub.2); oxide (O.sup.2-); hydroxide
(OH.sup.-); peroxo groups (O.sub.2.sup.2-); and superoxo groups
(O.sub.2.sup.-).
As discussed above, the properties of a particular
Co.sup.+3-containing complex can be altered by changing the
substituent groups on these general classes of valence stabilizers.
This can influence the effectiveness of corrosion inhibition
normally achieved using that specific complex.
4e) Mixed Inorganic/Organic Valence Stabilizers
Mixing inorganic and organic valence stabilizers in a conversion
coating solution will often result in a coating with poor corrosion
inhibiting properties because of cross interference. Inorganic and
organic stabilizers interact with Co.sup.+3 in different ways. For
example, inorganic valence stabilizers will perform their function
by forming a shell of octahedrally or tetrahedrally coordinated
anionic species around a captured Co.sup.+3 ion. Therefore, the net
charge of these inorganic Co.sup.+3-stabilizer complexes is always
negative. Organic species stabilize by the formation of a "soft
bond" between the bonding atom in the stabilizer (e.g., nitrogen or
sulfur) and the Co.sup.+3 ion. The net charge of these complexes is
usually positive. If these two very different types of
stabilization ligands are combined, then the magnitude of the
charge on the stabilized complex can be reduced significantly. The
performance of organic or inorganic stabilized corrosion inhibitor
complexes has been found to be directly related to the ability of
the complex to form and sustain a thick electrostatic barrier
layer. Additionally, a mixed stabilizer can have a poorly developed
electrostatic field and a non-optimal packing around the Co.sup.+3
ion, resulting in a complex with less resistance to aqueous attack.
Mixed organic/inorganic stabilized Co.sup.+3 coatings will
generally perform more poorly than coatings that have exclusively
organic or inorganic valence stabilizers for this reason.
4f) Valence Stabilizers for Tetravalent Cobalt
The Co.sup.+4 ion forms very few stable complexes with organic
compounds, and no currently known inorganically stabilized
complexes. Co.sup.+4 may be used in broader applications in the
future with compounds not currently identified. Examples of typical
organic ligands for Co.sup.+4 include dithiocarbamates,
dithiolenes, dithiols, dithioketones, norbornyls, biguamides, azo
oximes (including hydrazone oximes), some Schiff Bases, and some
azo compounds.
5) Additional Solubility Control Agents
One of the roles of the valence stabilizer is to allow for the
formation of a trivalent cobalt complex that has a specific
solubility range. The anions or cations present in the coating
solution maybe sufficient to form a Co 3-containing compound within
the conversion coating that exhibits the desired solubility
characteristics. However, additional solubility control may be
desirable to optimize the performance of the trivalent
cobalt-valence stabilizer complex. The use of an additional
solubility control agent is optional, not required.
Both the organic and inorganic valence stabilizers described above
may need some kind of additional solubility control that can be in
the form of either inorganic or organic compounds. The key to
selecting solubility control agents is to match the cationic or
anionic modifiers with individual Co.sup.+3-valence stabilizer
combinations. Some cations or anions may work to optimize one
Co.sup.+3-valence stabilizer complex, but this does not necessarily
mean they will optimize the solubility of a different complex.
The initial formation of a conversion coating may produce Co.sup.43
compounds with solubilities greater than optimal. A post-deposition
treatment can be applied to the coating as a remedial treatment or
as a desired process step. Additional solubility control agents
applied to a work piece can enhance the Co.sup.+3 content of the
coating by forming more insoluble compounds in place. Application
of a second solution after the conversion coating process has been
found to result in enhanced solubility control of Co.sup.+3 in the
conversion coating.
Additional solubility control agents are typically applied as a
second solution. Otherwise, these cations or anions would begin to
precipitate cobalt-containing compounds in the conversion coating
solution, depleting it of cobalt prior to treating the work piece.
In general, fine tuning of solubilityby cationic species is typical
for Co.sup.+3-stabilizer combinations when an inorganic valence
stabilizer is used, and by anionic species when an organic valence
stabilizer is used.
The need for an additional solubility control agent may be
illustrated for the situation where molybdate is used as a valence
stabilizer for a Co.sup.+3 conversion coating. Cationic species are
necessary to deposit a Co.sup.+3/molybdate complex within the
coating (the net charge on a Co.sup.+3/heteropolymolybdate anion
may either be -3 or -6). The cationic species needed to balance the
charge and form a compound is usually supplied from cations already
present in the conversion coating solution and/or by cations being
pulled into the solution from the work piece. However, if the
Co.sup.+3/molybdate complex composed of the available cations has a
much greater solubility than desired, then additional solubility
control agents will be required. The differences in effectiveness
of conversion coatings on various alloy compositions is likely a
reflection of the influence that the composition of the alloy
itselfhas on the solubility of the deposited conversion coating.
Similarly, anions present in a conversion coating solution or
source material will be incorporated in a Co.sup.+3 compound that
requires a negative charge balance. This is frequently observed
with Co.sup.+3/organic valence stabilizer combinations.
Additional solubility control can be achieved through the use
ofnon-toxic inorganic cations which include, but are not limited
to: H.sup.+, Li.sup.+, Na.sup.+, K.sup.+, Rb.sup.+, Cs.sup.+,
NH.sub.4.sup.+, Mg.sup.+2, Ca.sup.+2, Sr.sup.+2, Y.sup.+3,
La.sup.+3, Ce.sup.+3, Ce.sup.+4, Nd.sup.+3, Pr.sup.+3, Sc.sup.+3,
Sm.sup.+3, Eu.sup.+3, Eu.sup.+2, Gd.sup.+3, Tb.sup.+3, Dy.sup.+3,
Ho.sup.+3, Er.sup.+3, Tm.sup.+3, Yb.sup.+3, Lu.sup.+3, Ti.sup.+4,
Zr.sup.+4, Ti.sup.+3, Hf.sup.+4, Nb.sup.+4, Ta.sup.+4, Nb.sup.+4,
Ta.sup.+4, Mo.sup.+6, W.sup.+6, Mo.sup.+5, W.sup.+5, Mo.sup.+4,
W.sup.+4, Mn.sup.+2, Mn.sup.+3, Mn.sup.+4 Fe.sup.+2, Fe.sup.+3,
Co.sup.+2, Co.sup.+3, Ru.sup.+2, Ru.sup.+3, Ru.sup.+4, Rh.sup.+4,
Ir.sup.+3, Rh.sup.+2, Ir.sup.+2, Pd.sup.+4, Pt.sup.+4, Pd.sup.+2,
Pt.sup.+2, Cu.sup.+, Cu.sup.+2, Cu.sup.+3, Ag.sup.+, Ag.sup.+2,
Ag.sup.+3, Au.sup.+, Au.sup.+2, Au.sup.+3, Zn.sup.+2, Al.sup.+3,
Ga.sup.+3, Ga.sup.+, In.sup.+3, In.sup.+, Ge.sup.+4, Ge.sup.+2,
Sn.sup.+2, Sn.sup.+4, Sb.sup.+3, Sb.sup.+5, Bi.sup.+3, and
Bi.sup.+5. Any water-soluble compound that contains these cations
can be used for this purpose. Nitrates, chlorides, bromides, and
perchlorates of these cations offer inexpensive water-soluble
precursors, although many other water-soluble precursors exist.
Cationic solubility control may also be achieved through the use
ofnontoxic organic cations that include, but are not limited to:
quaternary ammonium compounds (NR.sub.4+, where R can be any
combination of alkyl, aromatic, or acyclic organic substituents,
such as the methyltriethylammonium ion); organics that contain at
least one N+site (such as pyridinium or thiazolium cations);
organics that contain at least one phosphonium site (P.sup.+, such
as the benzyltriphenylphosphonium ion); organics that contain at
least one stibonium site (Sb.sup.+, such as the
tetraphenylstibonium ion); organics that contain at least one
oxonium site (O.sup.+, such as pyrylium cations); organics that
contain at least one sulfonium site (S.sup.+, such as the
triphenylsulfonium ion); and organics that contain at least one
iodonium site (I.sup.+, such as the diphenyliodonium ion).
The quaternary ammonium compounds, organics containing at least one
N.sup.+ site, and organics containing at least one oxonium site are
the most important of these classifications because of the very
large number of stable cations that are available. Water-soluble
precursors for these organic cations are desirable in order to
maximize the amount of material available in the appropriate
conversion coating solution. Fluorides, chlorides, and bromides
offer the most water-soluble precursors for these organic cations,
although lower molecular weight nitrates and perchlorates of these
cations (e.g., tetramethylammonium) are also acceptable
water-soluble precursors. Larger molecular weight nitrates and
perchlorates are not generally acceptable as precursors because of
their low water solubility.
Although it is less desirable, toxic inorganic or organic cations
can be used as additional solubility control agents. Examples
oftoxic inorganic cations that can be used include, but are not
limited to: Be.sup.+2, Ba.sup.+2, V.sup.+5, V.sup.+4, V.sup.+3,
Cr.sup.+3, Ni.sup.+2, Ni.sup.+4, Os.sup.+4, Cd.sup.+2, Hg.sup.+1,
Hg.sup.+2, Tl.sup.+, Tl.sup.+3, As.sup.+3, As.sup.+5 Pb.sup.+2, and
Pb.sup.+4. Examples of toxic organic cations include, but are not
limited to: organic compounds that contain at least one arsonium
site (As.sup.+, an example being the tetraphenylarsonium ion) and
organic compounds that contain at least one selenonium site (Se, an
example being the triphenylselenonium ion). Use of these materials
for additional solubility control may be desirable in some specific
instances where the toxicity of the coating baths is of limited
importance to the operator. Water-soluble precursors for these
toxic cations are desirable in order to maximize the amount of
available cation for solubility control. In general, the nitrates,
fluorides, chlorides, bromides, and perchlorates of these cations
offer the highest water solubility.
Additional solubility control can also be achieved through the use
of nontoxic inorganic anions, especially for Co.sup.+3/organic
valence stabilizer combinations. Water-soluble precursors for these
inorganic anions are desirable in order to maximize the amount of
material available in the appropriate conversion coating solution.
These include, but are not limited to: fluorotitanates,
chlorotitanates, fluorozirconates, chlorozirconates,
fluoroniobates, chloroniobates, fluorotantalates, chlorotantalates,
molybdates, tungstates, permanganates, fluoromanganates,
chloromanganates, fluoroferrates, chloroferrates, fluorocobaltates,
chlorocobaltates, fluorozincates, chlorozincates, borates,
fluoroborates, fluoroaluminates, chloroaluminates, carbonates,
silicates, fluorosilicates, fluorostannates, nitrates, nitrites,
azides, phosphates, phosphites, phosphonates, phosphinites,
thiophosphates, thiophosphites, thiophosphonates, thiophosphinites,
fluorophosphates, fluoroantimonates, chloroantimonates, sulfates,
sulfites, sulfonates, thiosulfates, dithionites, dithionates,
fluorosulfates, tellurates, fluorides, chlorides, chlorates,
perchlorates, bromides, bromates, iodides, iodates, periodates, and
heteropolyanions (e.g., heteropolymolybdates,
silicomolybdates).
Additional solubility control can also be achieved through the use
of an almost unlimited number of non-toxic organic anions (e.g.,
organics with different carboxylates or acid groups). Examples
include, but are not limited to: ferricyanides; ferrocyanides;
cyanocobaltates; cyanocuprates; cyanomanganates; cyanates;
cyanatoferrates; cyanatocobaltates; cyanatocuprates;
cyanatomanganates; thiocyanates; thiocyanatoferrates;
thiocyanatocobaltates; thiocyanatocuprates; thiocyanatomanganates;
cyanamides; cyanamidoferrates; cyanamidocobaltates;
cyanamidocuprates; cyanamidomanganates; nitritoferrates;
nitritocobaltates; azides; (thio)carboxylates,
di(thio)carboxylates, tri(thio)carboxylates, or
tetra(thio)carboxylates [useful representatives including, but not
limited to, acetic acid, benzoic acid, succinic acid, fumaric acid,
salicylic acid, lactic acid, tartaric acid, antimonyl tartrates,
cinnamic acid, adipic acid, phthalic acid, terephthalic acid,
citric acid, ascorbic acid, malic acid, malonic acid, oxalic acid,
stearic acid, gallic acid, naphthenic acid, camphoric acid,
nitrosalicylic acid, aminosalicylic acid, acetylsalicylic acid,
sulfosalicylic acid, nitrobenzoic acid,
perfluoroC.sub.2-6carboxylic acids, trinitrobenzoic acid,
chlorobenzoic acid, anisic acid, iodobenzoic acid, anthranilic
acid, mandelic acid, toluic acid, nicotinic acid, isonicotinic
acid, pyrazolecarboxylic acid, picrolonic acid, quinaldic acid,
diphenic acid, benzoquinaldic acid, quinolinecarboxylic acid,
isoquinolinecarboxylic acid, triazinecarboxylic acid,
(thio)carbonic acids, (thio)carbamic acids, trimethylhexylic acid,
tetrafluorophthalic acid, ethylenediaminetetraacetic acid,
toluoylpropionic acid, lactobionic acid, octylthiopropionate,
lipoic acid, methylbenzoylpropionic acid, anthracenesuccinic acid,
benzothiazolecarboxylic acid, phenylacetic acid, glycolic acid,
thioglycolic acid, benzothiazolylthiosuccinic acid,
benzothiazolylthiopropionic acid, phenylanthranilic acid,
furancarboxylic acid, nitrofuroic acid,
phosphonobutanetricarboxylic acid, benzothiazolylthiosuccinic acid,
N-phosphonomethylglycine, cresoxyacetic acid, aminobutyric acid,
alanine, asparagine, cysteine, glutamine, glycine, leucine,
methionine, phenylalanine, proline, serine, threonine, tryptophan,
tyrosine, valine, glutamic acid, aspartic acid, arginine,
histidine, lysine, trihydroxyglutaric acid, phenoxyacetic acid,
hydroxynaphthoic acid, phenylbutyric acid, hydroxyphosphonoacetic
acid, tropic acid, aminophenylpropionic acid, dihydrocinnainic
acid, hydroxycinnamic acid, cinchomeronic acid, aurintricarboxylic
acid, benzotriazolecarboxylic acid, hydroxyphosphonoacetic acid,
cyanuric acid, barbituric acid, violuric acid, diphenylvioluric
acid, dilituric acid, thiobarbituric acid, cresotic acid,
trimethylhexylic acid, nitrilotriacetic acid,
N,N'-terephthaloylbis(aminocaproic acid),
ethyleneglycolbis(aminoethylether)tetraacetic acid,
diethylenetriaminepentaacetic acid, 2-phosphonobutanetricarboxylic
acid, N,N'-bis(2-hydroxysuccinyl)ethylenediamine, nicotinic acid,
naptalam, nitrobenzoic acid, nonylphenoxyacetic acid, and
olsalazine]; (thio)pbenolates, di(thio)phenolates,
tri(thio)phenolates, or tetra(thio)phenolates [useful
representatives including, but not limited to, pyrocatechol,
resorcinol, picric acid, styphnic acid, pyrogallol, purpurin,
purpurogallin, benzopurpurin, gallein, thiophenol, rhodizonic acid,
kojic acid, chromotropic acid, carminic acid, fluorescein, tannic
acid, and humic acid]; (thio)phosphonates, di(thio)phosphonates, or
tri(thio)phosphonates [useful representatives including, but not
limited to, diethylphosphonic acid, diphenylphosphonic acid,
nitrophenylphosphonic acid, perfluoroC.sub.2-16phosphonic acids,
benzenephosphonic acid, phytic acid, hydroxyethylidenebisphosphonic
acid, nitrilotrimethylenephosphonic acid, aminomethylenephosphonic
acid, etidronic acid, ethylphosphonic acid, chloroethylphosphonic
acid, ethylenediaminotetramethylenephosphonic acid,
laurylhydroxydiphosphonic acid, methylaminodimethylenephosphonic
acid, alkyl(aryl)diphosphonic acids, N-cetylaminoethanediphosphonic
acid, carboxyhydroxymethylphosphonic acid (hpa),
oxyethylidenediphosphonic acid, polycaproamidophosphonates,
phenylethanetriphosphonic acid, oxidronic acid, and pamidronic
acid]; (thio)phosphonamides, di(thio)phosphonamides, or
tri(thio)phosphonamides [useful representatives including, but not
limited to, phosphoramidic acid, phosphordiamidic acid
(diamidophosphonic acid), and phosphoramidothioic acid];
amino(thio)phosphonates, diamino(thio)phosphonates, or
triamino(thio)phosphonates; imino(thio)phosphonates or
diimino(thio)phosphonates; (thio)sulfonates, di(thio)sulfonates, or
tri(thio)sulfonates [useful representatives including, but not
limited to, methanesulfonic acid, benzenesulfonic acid,
aminobenzenesulfonic acid (sulfanilic acid), nitrobenzenesulfonic
acid, phenylsulfonic acid, naphthalenesulfonic acid,
nitronaphthalenesulfonic acid, oxinesulfonic acid, alizarinsulfonic
acid, benzidinesulfonic acid, flavianic acid, camphorsulfonic acid,
diiodophenolsulfonic acid (sozoiodol),
8-hydroxyquinoline-5-sulfonic acid,
7-nitro-8-hydroxyquinoline-5-sulfonic acid, benzotriazolesulfonic
acid, bis(trifluoromethyl)bcnzenesulfonic acid,
diiododihydroxybenzophenonesulfonic acid,
p-amino-p'-ethoxydiphenylamine-o-sulfonic acid,
1-amino-2-naphthol-4-sulfonic acid,
1,2-diaminoanthraquinone-3-sulfonic acid,
1,5-dinitro-2-naphthol-7-sulfonic acid, perfluoroC.sub.2-16sulfonic
acids, benzenedisulfonic acid, phenyldisulfonic acid,
naphthalenedisulfonic acid, 3,6-naphtholdisulfonic acid,
indigodisulfonic acid, benzidinedisulfonic acid,
carboxyiodobenzenesulfonic acids, N-benzeneaminomethanesulfonic
acid (ams), amido-G-acid, amido-R-acid, naphthalene(di)sulfonic
acid (Armstrong's acid), amsonic acid, Badische acid,
camphorsulfonic acid, chrysophenine, Cassella's acid, chromotropic
acid, Cleve's acid, croceic acid, anthracenesulfonic acid,
hydroxyquinolinesulfonic acid, hydrazinobenzenesulfonic acid,
indigo carmine, indoxyl, isatinsulfonic acid, indican,
lignosulfonic acid, metanil yellow, metanilic acid,
naphthoquinonesulfonic acid, Nuclear Fast Red, naphthol(di)sulfonic
acid, naphthylamine(di)sulfonic acid, Orange I, orthanilic acid,
phenol(di)sulfonic acid, methylenedinaphthalenesulfonic acid,
methyl orange, and piperazinediethanesulfonic acid (pipes)];
(thio)sulfonamides, di(thio)sulfonamides, or tri(thio)sulfonamides;
amino(thio)sulfonates, diamino(thio)sulfonates, or
triamino(thio)sulfonates; imino(thio)sulfonates (including
sulfamates) or diimino(thio)sulfonates (including disulfamates)
[useful representatives including, but not limited to,
methylsulfamic acid and phenylsulfamic acid]; (thio)borates,
di(thio)borates, or (thio)boronates [useful representatives
including, but not limited to, phenylboric acid and borotartaric
acid]; organic silicates; and stibonates [useful representatives
including, but not limited to, antimonyl tartrate and
benzenestibonic acid]. Water-soluble precursors for these organic
anions are desirable to maximize the amount available in the
appropriate conversion coating solution.
Finally, toxic inorganic or organic anions can be used as
additional solubility control agents, although this is less
desirable. Examples oftoxic inorganic anions include, but are not
limited to: arsenates, arsenites, fluoroarsenates, chloroarsenates,
selenates, selenites, fluorothallates, chlorothallates, iodomercury
anions (e.g., Nessler's reagent), thiocyanatomercury anions (e.g.,
Behren's reagent), chloromercurates, bromomercurates, osmates,
fluoronickelates, chromates, Reinecke's salt, and vanadates.
Examples of toxic organic anions include cyanides; cyanochromates;
cyanonickelates; cyanatochromates; cyanatonickelates;
thiocyanatochromates; thiocyanatonickelates; cyanamidochromates;
cyanamidonickelates; nitritonickelates; arsonates, diarsonates, or
triarsonates [useful representatives including, but not limited to,
propylarsonic acid, phenylarsonic acid, hydroxyphenylarsonic acid,
benzenearsonic acid, methylbenzenearsonic acid,
hydroxybenzenearsonic acid, and nitrobenzenearsonic acid]; organic
selenates, diselenates, or triselenates. These materials may be
necessary in some specific instances for additional solubility
control where coating bath toxicity is of limited importance.
Water-soluble precursors for these anions are desirable in order to
maximize the amount of available anion to interact with the
Co.sup.+3 complex. The alkali or ammonium species of these anions
typically offer the greatest water solubility.
6) Agents to Increase Color-Fastness of Coating
Conversion coatings will frequently be colored to improve the
aesthetic nature of the work piece, as well as to aid in the
identification of coated versus uncoated areas. Long-term exposure
to high energy wavelengths (i.e., the ultraviolet wavelengths of
sunlight) may fade or dim the color of the coated work piece. The
conversion coating solution may include agents that improve the
color-fastness of the coating. Typically, these are termed "UV
blockers" in the paint and coatings literature. Active UV blockers
are typically dark in color and function by absorbing nearly all of
the light energy. Passive UV blockers are light in color and
function by reflecting back nearly all of the light energy.
Examples of active UV blockers include carbon black, graphite and
phthalocyanines. Examples of passive UV blockers include titanium
oxide, tin oxide, silicon oxide, silicates, or
aluminosilicates.
B. Solution Composition and Preparation
Additional important process considerations include chemical
concentrations, pH of the coating solution, redox potential of the
coating solution, application temperature, and contact time.
1) Solvents
Water is a typical solvent for these conversion coating solutions
due to its availability and low cost. Other solvents or
combinations of water with other solvents (such as alcohols,
ketones, etc.) may also be used if desired. However, these
processes will be more costly than those using water
exclusively.
2) Cobalt Concentration
The maximum concentration of the cobalt source depends upon the
solubility of the specific cobalt source used. Any concentration
exceeding this precursor solubility will result in undissolved
solid material that will not be incorporated into the conversion
coating and may even act as flaws in the coating. The ambient
temperature processes outlined here produce Co.sup.+3 conversion
coatings with exceptional corrosion inhibiting character.
Therefore, the solubility of the cobalt sources in water at or near
ambient temperature (25.degree. C.) should be the maximum amount of
the cobalt source that is added. Since the solubility of virtually
all materials in water increases with temperature, more cobalt can
be added to the conversion coating solution if the temperature of
the bath is increased from ambient. Although higher temperatures
lead to higher allowable concentrations of cobalt precursors, this
is unnecessary and adds to the cost of the process.
Acidic pHs will typically increase the solubility of many inorganic
materials, thereby increasing the concentration of cobalt available
in solution. A general estimate of the maximum concentration of
cobalt in the conversion coating solution at ambient conditions can
be determined from the solubilities of some of the more desirable
cobalt sources as listed in Table 3.
TABLE-US-00004 TABLE 3 Solubilities of Some Cobalt Sources under
Ambient Conditions [Maximum Concentration of Cobalt in Solution]
(at or near 25.degree. C. and at or near pH 7) Cobalt Source
Solubility in Water (mole/L) Cobalt (II) nitrate 5.1 .times.
10.sup.0 Cobalt (II) sulfate 2.3 .times. 10.sup.0 Cobalt (II)
perchlorate 7.08 .times. 10.sup.0 Cobalt (II) chloride 3.46 .times.
10.sup.0 Cobalt (II) fluoride .sup. 1.55 .times. 10.sup.-1 Cobalt
(II) bromide 3.05 .times. 10.sup.0 Cobalt (II) iodide 1.08 .times.
10.sup.1 Cobalt (II) bromate 1.08 .times. 10.sup.0 Cobalt (II)
chlorate 1.67 .times. 10.sup.1 Cobalt (II) hexafluorosilicate 3.8
.times. 10.sup.0 Cobalt (II) formate .sup. 2.7 .times. 10.sup.-1
Cobalt (II) acetate ~10.sup.0 Cobalt (II) propionate 1.3 .times.
10.sup.0 Cobalt (II) butyrate ~10.sup.0 Cobalt (II) benzoate
~10.sup.0 Hexaammine cobalt (III) chloride .sup. 2.2 .times.
10.sup.-1 Hexaammine cobalt (III) nitrate .sup. 4.9 .times.
10.sup.-2 Pentaammine cobalt (III) chloride .sup. 9.3 .times.
10.sup.-1
The depletion of cobalt from the coating solution below an
acceptable level is a function of the amount of metal surface area
being coated prior to regeneration of the solution. A coating
applied to a very large surface area may deplete the solution to
the point that subsequent solution applications no longer form
effective coatings. Less cobalt will be removed from the conversion
coating solution when treating a smaller surface area of metal, so
more work pieces can be coated from the same solution.
The corrosion-inhibiting cobalt compounds formed on the surface of
the metal exhibit solubilities ranging from approximately
5.times.10.sup.-2 to 5.times.10.sup.-5 moles/liter of cobalt in
water. Coating solutions with cobalt concentrations much less than
these concentrations may: 1) withdraw cobalt from the formed
coating in order to attempt to reach an equilibrium, or 2) may
produce an incomplete, poorly formed oxide film. Intentionally
exhausted (depleted) conversion coating solutions have been
observed to degrade a coated surface and return cobalt to the
coating solution. The lowest concentration of cobalt in the
precursor conversion coating bath from which some resultant
corrosion inhibition will be exhibited is probably in the range of
1.times.10.sup.-3 to 1.times.10.sup.-4 moles/liter of cobalt. We
used cobalt concentrations of approximately 1.times.10.sup.-1
mole/liter of cobalt with excellent results.
3) Oxidizer Concentration
The concentration of the oxidizer source can range up to the
maximum solubility of the specific oxidizer source used. Any
concentration exceeding this solubility will result in undissolved
solid material that will not be available to raise the redox
potential of the conversion coating solution. This process is
designed to operate at ambient temperatures, so the maximum
concentration of oxidizer source should be restricted to its
maximum solubility in water at or near ambient temperature
(25.degree. C.). As discussed above, more oxidizer can be added to
the conversion coating solution ifthe temperature of the bath is
increased from ambient. Higher temperatures may lead to higher
allowable concentrations of oxidizer precursors, but this is
unnecessary and undesirable in light of process economics. Table 4
shows the solubilities in water of some of the more desirable
oxidizer sources.
TABLE-US-00005 TABLE 4 Solubilities of Some Oxidizer Sources under
Ambient Conditions (At or near 25.degree. C. and at or near pH 7)
Solubility in Oxidizer Source Example Precursor Water (mole/L) A)
Peroxides and Hydrogen peroxide 60 wt. % Superoxides Lithium
peroxide .sup. ~1 .times. 10.sup.0.sup. Sodium peroxide .sup. ~1
.times. 10.sup.0.sup. Potassium superoxide .sup. ~1 .times.
10.sup.0.sup. B) Persulfates Ammonium persulfate 2.6 .times.
10.sup.0 Lithium persulfate .sup. ~3 .times. 10.sup.0.sup. Sodium
persulfate 3.1 .times. 10.sup.0 Potassium persulfate .sup. 2.0
.times. 10.sup.-1 Magnesium persulfate .sup. ~1 .times.
10.sup.1.sup. Calcium persulfate .sup. ~1 .times. 10.sup.1.sup.
Strontium persulfate .sup. ~5 .times. 10.sup.0.sup. Barium
persulfate 1.3 .times. 10.sup.0 C) Perborates Ammonium perborate
.sup. 1.8 .times. 10.sup.-1 Lithium perborate .sup. ~1 .times.
10.sup.-1 Sodium perborate .sup. 1.7 .times. 10.sup.-1 Potassium
perborate .sup. 1.1 .times. 10.sup.-1 D) Peroxybenzoates
Monoperoxyphthalic acid .sup. ~1 .times. 10.sup.-1 Magnesium .sup.
~1 .times. 10.sup.-1 monoperoxyphthalate Chloroperoxybenzoic acid
.sup. ~1 .times. 10.sup.-1 E) Chlorites Lithium chlorite .sup. ~5
.times. 10.sup.0.sup. Sodium chlorite 4.3 .times. 10.sup.0 Calcium
chlorite .sup. ~1 .times. 10.sup.0.sup. Strontium chlorite .sup. ~5
.times. 10.sup.-1 Barium chlorite .sup. ~1 .times. 10.sup.-1 F)
Bromates Ammonium bromate .sup. ~1 .times. 10.sup.1.sup. Lithium
bromate 4.85 .times. 10.sup.0 Sodium bromate 1.82 .times. 10.sup.0
Potassium bromate .sup. 8.0 .times. 10.sup.-1 Rubidium bromate
.sup. 1.4 .times. 10.sup.-1 Cesium bromate .sup. 1.4 .times.
10.sup.-1 Magnesium bromate 1.0 .times. 10.sup.0 Calcium bromate
.sup. ~ 1 .times. 10.sup.0 Strontium bromate .sup. 9.1 .times.
10.sup.-1 Zinc bromate .sup. ~1 .times. 10.sup.0.sup. Ferric
bromate .sup. ~1 .times. 10.sup.0.sup. G) Hypochlorites Lithium
hypochlorite .sup. ~1 .times. 10.sup.1.sup. Sodium hypochlorite
.sup. ~1 .times. 10.sup.1.sup. Magnesium hypochlorite .sup. ~1
.times. 10.sup.1.sup. Calcium hypochlorite .sup. ~1 .times.
10.sup.1.sup. Strontium hypochlorite .sup. ~5 .times. 10.sup.0.sup.
Barium hypochlorite .sup. ~5 .times. 10.sup.0.sup. H) Periodates
Periodic acid 4.96 .times. 10.sup.1 Ammonium periodate .sup. 1.3
.times. 10.sup.-1 Lithium periodate .sup. ~1 .times. 10.sup.0.sup.
Sodium periodate .sup. 6.7 .times. 10.sup.-1 Potassium periodate
.sup. 2.9 .times. 10.sup.-2 Rubidium periodate .sup. 2.4 .times.
10.sup.-2 Cesium periodate .sup. 6.6 .times. 10.sup.-2 Magnesium
periodate .sup. ~1 .times. 10.sup.-2 I) Permanganates Ammonium
permanganate .sup. 5.77 .times. 10.sup.-1 Lithium permanganate 3.97
.times. 10.sup.0 Sodium permanganate .sup. ~1 .times. 10.sup.0.sup.
Potassium permanganate .sup. 4.04 .times. 10.sup.-1 Magnesium
permanganate .sup. ~1 .times. 10.sup.1.sup. Calcium permanganate
9.18 .times. 10.sup.0 Strontium permanganate 7.67 .times. 10.sup.0
Barium permanganate 2.01 .times. 10.sup.0 Zinc permanganate .sup.
8.10 .times. 10.sup.-1 Ferric permanganate .sup. ~1 .times.
10.sup.0.sup. J) Chlorates Lithium chlorate 5.5 .times. 10.sup.1
Sodium chlorate 7.5 .times. 10.sup.0 Potassium chlorate .sup. 5.8
.times. 10.sup.-1 Rubidium chlorate .sup. 3.0 .times. 10.sup.-1
Cesium chlorate .sup. 2.9 .times. 10.sup.-1 Magnesium chlorate 4.3
.times. 10.sup.0 Calcium chlorate 7.4 .times. 10.sup.0 Strontium
chlorate 6.9 .times. 10.sup.0 Zinc chlorate 8.6 .times. 10.sup.0
Barium chlorate .sup. 8.5 .times. 10.sup.-1 K) Perchlorates
Perchloric acid 75 wt. % Ammonium perchlorate 1.3 .times. 10.sup.0
Lithium perchlorate 5.6 .times. 10.sup.0 Sodium perchlorate 1.5
.times. 10.sup.1 Potassium perchlorate .sup. 3.6 .times. 10.sup.-1
Rubidium perchlorate .sup. 2.2 .times. 10.sup.-1 Cesium perchlorate
.sup. 8.6 .times. 10.sup.-2 Magnesium perchlorate 4.4 .times.
10.sup.0 Calcium perchlorate 7.9 .times. 10.sup.0 Strontium
perchlorate 1.1 .times. 10.sup.1 Zinc perchlorate .sup. ~1 .times.
10.sup.0.sup. Barium perchlorate 5.1 .times. 10.sup.0 Aluminum
perchlorate .sup. ~1 .times. 10.sup.0.sup. Ferric perchlorate .sup.
~1 .times. 10.sup.0.sup. Tetramethylammonium .sup. ~1 .times.
10.sup.0.sup. perchlorate Tetraethylammonium .sup. ~5 .times.
10.sup.-1 perchlorate Tetrapropylammonium .sup. ~1 .times.
10.sup.-1 perchlorate L) Nitrates Nitric acid 75 wt. % Ammonium
nitrate 2.5 .times. 10.sup.1 Lithium nitrate 1.3 .times. 10.sup.1
Sodium nitrate 1.1 .times. 10.sup.1 Potassium nitrate 7.4 .times.
10.sup.0 Rubidium nitrate 3.0 .times. 10.sup.0 Cesium nitrate 2.1
.times. 10.sup.0 Magnesium nitrate 4.9 .times. 10.sup.0 Calcium
nitrate 2.1 .times. 10.sup.1 Strontium nitrate 3.4 .times. 10.sup.0
Zinc nitrate 6.2 .times. 10.sup.0 Barium nitrate .sup. 3.3 .times.
10.sup.-1 Aluminum nitrate 1.7 .times. 10.sup.0 Ferric nitrate 5.7
.times. 10.sup.0 Tetramethylammonium .sup. ~1 .times. 10.sup.1.sup.
nitrate Tetraethylammonium .sup. ~5 .times. 10.sup.0.sup. nitrate
Tetrapropylammonium .sup. ~1 .times. 10.sup.0.sup. nitrate
Tetrabutylammonium .sup. ~5 .times. 10.sup.-1 nitrate M) Nitrites
Lithium nitrite 2.8 .times. 10.sup.1 Sodium nitrite 1.3 .times.
10.sup.1 Potassium nitrite 3.5 .times. 10.sup.1 Magnesium nitrite
.sup. ~1 .times. 10.sup.0.sup. Calcium nitrite 3.9 .times. 10.sup.0
Strontium nitrite 3.8 .times. 10.sup.0 Zinc nitrite .sup. ~1
.times. 10.sup.0.sup. Barium nitrite 2.9 .times. 10.sup.0 N)
Vanadates Vandium pentoxide .sup. 4.4 .times. 10.sup.-2 Ammonium
vanadate .sup. 4.4 .times. 10.sup.-2 Lithium vanadate .sup. ~1
.times. 10.sup.0.sup. Sodium vanadate 1.7 .times. 10.sup.0
Potassium vanadate .sup. ~1 .times. 10.sup.0.sup. Magnesium
vanadate .sup. ~1 .times. 10.sup.0.sup. Calcium vanadate .sup. ~5
.times. 10.sup.-1 O) Iodates Iodic acid 1.76 .times. 10.sup.1
Iodine pentoxide 5.6 .times. 10.sup.0 Ammonium iodate .sup. 1
.times. 10.sup.-1 Lithium iodate 4.4 .times. 10.sup.0 Sodium iodate
.sup. 4.5 .times. 10.sup.-1 Potassium iodate .sup. 2.2 .times.
10.sup.-1 Magnesium iodate .sup. 2.3 .times. 10.sup.-1
Low oxidizer concentrations may not oxidize a sufficient quantity
of cobalt from the divalent state to the trivalent state. This
would result in reduced corrosion inhibiting performance. The net
redox potential of the coating solution is also a function of the
surface area of the metal that has been coated. The redox potential
decreases over time (e.g., several days), so these solutions
require additions of oxidizer to maintain the redox potential.
4) Preparative Agent Concentration
The concentration of the preparative agent is desirable for the
conversion coating process. Cratering of the coated metal surface
has been found when the solution concentration of the preparative
agent exceeds (or even approaches) the solubility of the precursor
material. This cratering results in coatings with reduced corrosion
resistance Solubility values for many fluorides (a typical
preparative agent) are given in Table 5. The added concentrations
should not exceed (or come close to) these values. Of course,
variations in the solution temperature and pH will change the
solubilities of each of these preparative agents, but the values
given below can be used as general approximations.
TABLE-US-00006 TABLE 5 Solubilities of Fluoride Preparative Agents
under Ambient Conditions [Maximum Allowable Concentrations in
Solution] (At or near 25.degree. C. and at near pH 7) Solubility in
Water Fluoride Source Example Precursor (mole/L) A) Simple
Fluorides Hydrofluoric acid 75 wt. % Ammonium fluoride 2.7 .times.
10.sup.1 .sup. Lithium fluoride 1.04 .times. 10.sup.-1.sup. Sodium
fluoride .sup. 1.01 .times. 10.sup.0 Potassium fluoride .sup. 1.59
.times. 10.sup.1 Potassium bifluoride .sup. 5.25 .times. 10.sup.0
Rubidium fluoride .sup. 1.25 .times. 10.sup.1 Cesium fluoride .sup.
2.42 .times. 10.sup.1 Copper (II) fluoride 4.62 .times.
10.sup.-1.sup. Silver (I) fluoride .sup. 1.43 .times. 10.sup.1 Zinc
fluoride 1.57 .times. 10.sup.-1.sup. Aluminum fluoride .sup. 6.6
.times. 10.sup.-2.sup. Titanium fluoride ~1 .times. 10.sup.0.sup.
Zirconium fluoride .sup. 8.3 .times. 10.sup.-2.sup. Germanium
fluoride hydrate ~1 .times. 10.sup.-1 Tin (II) fluoride ~1 .times.
10.sup.-1 Tin (IV) fluoride ~1 .times. 10.sup.0.sup. Vanadium
fluoride ~1 .times. 10.sup.-1 Niobium fluoride ~1 .times.
10.sup.0.sup. Tantalum fluoride ~1 .times. 10.sup.-1 Antimony (III)
fluoride 3.15 .times. 10.sup.-1.sup. Antimony (V) fluoride ~1
.times. 10.sup.1.sup. Manganese (II) fluoride .sup. 7.1 .times.
10.sup.-2.sup. Cobalt (II) fluoride 1.55 .times. 10.sup.-1.sup. B)
Hexafluorozirconates Ammonium hexafluorozirconate ~1 .times.
10.sup.-1 Lithium hexafluorozirconate ~8 .times. 10.sup.-2 Sodium
hexafluorozirconate ~6 .times. 10.sup.-2 Potassium
hexafluorozirconate 8.12 .times. 10.sup.-2.sup. Rubidium
hexafluorozirconate 8.48 .times. 10.sup.-2.sup. Cesium
hexafluorozirconate 1.12 .times. 10.sup.-1.sup. C)
Hexafluorotitanates Ammonium hexafluorotitanate ~1 .times.
10.sup.-1 Lithium hexafluorotitanate ~5 .times. 10.sup.-2 Sodium
hexafluorotitanate ~1 .times. 10.sup.-2 Potassium
hexafluorotitanate .sup. 6.0 .times. 10.sup.-2.sup. Rubidium
hexafluorotitanate .sup. 2.5 .times. 10.sup.-2.sup. Cesium
hexafluorotitanate .sup. 5.5 .times. 10.sup.-2.sup. D)
Hexafluorosilicates Ammonium hexafluorosilicate .sup. 1.04 .times.
10.sup.0 Lithium hexafluorosilicate 3.8 .times. 10.sup.0 .sup.
Sodium hexafluorosilicate .sup. 3.5 .times. 10.sup.-2.sup.
Potassium hexafluorosilicate .sup. 5.5 .times. 10.sup.-3.sup.
Rubidium hexafluorosilicate .sup. 6.9 .times. 10.sup.-3.sup. Cesium
hexafluorosilicate .sup. 2.3 .times. 10.sup.-2.sup. Silver (I)
hexafluorosilicate ~1 .times. 10.sup.-0 Magnesium
hexafluorosilicate 3.9 .times. 10.sup.0 .sup. Calcium
hexafluorosilicate ~1 .times. 10.sup.-1 Strontium
hexafluorosilicate .sup. 1.2 .times. 10.sup.-1.sup. Zinc
hexafluorosilicate ~1 .times. 10.sup.0.sup. Copper (II)
hexafluorosilicate 7.4 .times. 10.sup.0 .sup. Cobalt (II)
hexafluorosilicate .sup. 3.82 .times. 10.sup.0 Manganese (II)
hexaluorosilicate .sup. 4.59 .times. 10.sup.0 Iron (II)
hexafluorosilicate .sup. 4.19 .times. 10.sup.0 Iron (III)
hexafluorosilicate .sup. 4.19 .times. 10.sup.0 E)
Hexafluoroaluminates Ammonium hexafluoroaluminate .sup. 5.3 .times.
10.sup.-2.sup. Lithium hexafluoroaluminate .sup. 6.6 .times.
10.sup.-3.sup. Sodium hexafluoroaluminate .sup. 2.9 .times.
10.sup.-3.sup. Potassium hexafluoroaluminate .sup. 6.1 .times.
10.sup.-3.sup. F) Tetrafluoroborates Ammonium tetrafluoroborate 2.4
.times. 10.sup.0 .sup. Lithium tetrafluoroborate ~1 .times.
10.sup.0.sup. Sodium tetrafluoroborate 9.8 .times. 10.sup.0 .sup.
Potassium tetrafluoroborate .sup. 3.5 .times. 10.sup.-2.sup. G)
Hexafluorogermanates Ammonium hexafluorogermanates ~1 .times.
10.sup.-1 Potassium hexafluorogermanates .sup. 2.0 .times.
10.sup.-2.sup. Rubidium hexafluorogermanates ~1 .times. 10.sup.-2
Cesium hexafluorogermanates ~1 .times. 10.sup.-2 H)
Hexafluorostannates Ammonium hexafluorostannate ~1 .times.
10.sup.-1 Lithium hexafluorostannate ~1 .times. 10.sup.-2 Sodium
hexafluorostannate ~1 .times. 10.sup.-2 Potassium
hexafluorostannate 1.28 .times. 10.sup.-1.sup. Rubidium
hexafluorostannate .sup. 6.2 .times. 10.sup.-2.sup. Cesium
hexafluorostannate .sup. 7.9 .times. 10.sup.-2.sup. I)
Hexafluorohafnates Ammonium hexafluorohafnate ~1 .times.
10.sup.0.sup. Lithium hexafluorohafnate ~1 .times. 10.sup.-1 Sodium
hexafluorohafnate ~7 .times. 10.sup.-2 Potassium hexafluorohafnate
.sup. 1.3 .times. 10.sup.-1.sup. Rubidium hexafluorohafnate .sup.
1.9 .times. 10.sup.-1.sup. Cesium hexafluorohafnate .sup. 1.7
.times. 10.sup.-1.sup. J) Hexafluorogallates Ammonium fluorogallate
~1 .times. 10.sup.-2 Alkali/Alkaline fluorogallates ~1 .times.
10.sup.-2 Silver (I) fluorogallate ~1 .times. 10.sup.0.sup. Copper
(II) fluorogallate ~1 .times. 10.sup.-2 Zinc fluorogallate ~1
.times. 10.sup.-1 Manganese (II), iron (II), and ~1 .times.
10.sup.-2 cobalt (II) fluorogallates K) Hexafluorophosphates
Ammonium hexafluorophosphate ~1 .times. 10.sup.0.sup. Lithium
hexafluorophosphate ~2 .times. 10.sup.0.sup. Sodium
hexafluorophosphate 5.6 .times. 10.sup.0 .sup. Potassium
hexafluorophosphate .sup. 5.1 .times. 10.sup.-1.sup. Rubidium
hexafluorophosphate ~1 .times. 10.sup.-1 Cesium hexafluorophosphate
~1 .times. 10.sup.-1 L) Hexafluoroantimonates Ammonium
hexafluoroantimonate 4.7 .times. 10.sup.0 .sup. Lithium
hexafluoroantimonate ~1 .times. 10.sup.0.sup. Sodium
hexafluoroantimonate .sup. 4.97 .times. 10.sup.0 Potassium
hexafluoroantimonate 3.7 .times. 10.sup.0 .sup. Rubidium
hexafluoroantimonate 1.6 .times. 10.sup.0 .sup. Cesium
hexafluoroantimonate ~5 .times. 10.sup.0.sup. M)
Heptafluoroniobates Lithium heptafluoroniobate ~5 .times. 10.sup.-1
Sodium heptafluoroniobate ~5 .times. 10.sup.-2 Potassium
heptafluoroniobate .sup. 2.6 .times. 10.sup.-1.sup. Rubidium
heptafluoroniobate ~1 .times. 10.sup.-1 Cesium heptafluoroniobate
~3 .times. 10.sup.-1 N) Heptafluorotantalates Lithium
heptafluorotantalate ~5 .times. 10.sup.-1 Sodium
heptafluorotantalate ~5 .times. 10.sup.-2 Potassium
heptafluorotantalate ~3 .times. 10.sup.-1 Rubidium
heptafluorotantalate ~1 .times. 10.sup.-1 Cesium
heptafluorotantalate ~3 .times. 10.sup.-1
The concentration of preparative agent must be sufficient to treat
the selected surface because the preparative agent initiates the
entire coating process. Low fluoride ion concentrations result in
thin coatings that do not exhibit an acceptable degree of corrosion
inhibition. The substrate metal remains smooth and bright, and no
visible coating action takes place at very low fluoride ion
concentrations. These effects were found to begin when the ratio of
fluoride ions to cobalt ions in the coating solution falls below a
ratio of 0.05. Therefore, the minimum recommended
fluoride-to-cobalt ratio is 0.05.
5) Valence Stabilizer Concentration
The concentration of the valence stabilizer can be any
concentration up to the maximum solubility of the specific valence
stabilizer source used. Any concentration exceeding this solubility
will result in undissolved solid material that will not be
available for stabilizing the desired trivalent cobalt ions. Since
this process was developed to operate at ambient temperature, the
concentration of valence stabilizer source should be restricted to
its maximum solubility in water at or near ambient temperature
(25.degree. C.). Higher temperatures may allow more valence
stabilizer to be added to the conversion coating solution, but this
is unnecessary and adds additional cost to the process. Table 6
shows the aqueous solubilities of some of the more desirable
sources for wide band (typical) inorganic valence stabilizers, and
Table 7 shows the aqueous solubilities of some sources for narrow
band (less typical) inorganic valence stabilizers.
TABLE-US-00007 TABLE 6 Solubilities of Wide Band Inorganic Valence
Stabilizer Precursors under Ambient Conditions [Maximum Allowable
Concentrations in Solution] (At or near 25.degree. C. and at or
near pH 7) Inorganic Solubility Valence in Water Stabilizer Example
Precursors (mole/L) Molybdates Molybdenum trioxide 7.4 .times.
10.sup.-3 Molybdic acid 7.4 .times. 10.sup.-3 Ammonium molybdate ~5
.times. 10.sup.0.sup. Lithium molybdate ~1 .times. 10.sup.1.sup.
Sodium molybdate 2.15 .times. 10.sup.2 .sup. Potassium molybdate
7.75 .times. 10.sup.2 .sup. Rubidium molybdate 6.4 .times.
10.sup.0.sup. Cesium molybdate 4.8 .times. 10.sup.0.sup. Magnesium
molybdate 7.4 .times. 10.sup.-1 Tungstates Tungstic acid 8.0
.times. 10.sup.-1 Ammonium tungstate ~1 .times. 10.sup.2.sup.
Lithium tungstate 5.8 .times. 10.sup.1.sup. Sodium tungstate 2.49
.times. 10.sup.2 .sup. Potassium tungstate 1.42 .times. 10.sup.2
.sup. Rubidium tungstate ~5 .times. 10.sup.1.sup. Cesium tungstate
~5 .times. 10.sup.0.sup. Magnesium tungstate hydrate 7.2 .times.
10.sup.-1 Vanadates Vanadium pentoxide 4.4 .times. 10.sup.-2
Ammonium vanadate 4.4 .times. 10.sup.-2 Lithium vanadate ~1 .times.
10.sup.0.sup. Sodium vanadate 1.7 .times. 10.sup.0.sup. Potassium
vanadate ~1 .times. 10.sup.0.sup. Rubidium vanadate .sup. ~5
.times. 10.sup.-1.sup. Cesium vanadate .sup. ~5 .times.
10.sup.-1.sup. Magnesium vanadate ~1 .times. 10.sup.0.sup. Calcium
vanadate .sup. ~5 .times. 10.sup.-1.sup. Niobates Ammonium niobate
.sup. ~1 .times. 10.sup.-1.sup. Lithium niobate .sup. ~1 .times.
10.sup.-1.sup. Sodium niobate 5.9 .times. 10.sup.-2 Potassium
niobate .sup. ~5 .times. 10.sup.-2.sup. Magnesium hexaniobate 8.8
.times. 10.sup.-2 Calcium hexaniobate 4.7 .times. 10.sup.-2
Tantalates Ammonium tantalate .sup. ~1 .times. 10.sup.-2.sup.
Lithium tantalate .sup. ~1 .times. 10.sup.-2.sup. Sodium tantalate
5.5 .times. 10.sup.-3 Potassium tantalate .sup. ~5 .times.
10.sup.-3.sup. Tellurates Telluric acid .sup. ~5 .times.
10.sup.-1.sup. Ammonium tellurate .sup. ~5 .times. 10.sup.-1.sup.
Lithium tellurate ~1 .times. 10.sup.0.sup. Sodium tellurate 2.8
.times. 10.sup.-2 Potassium tellurate .sup. ~1 .times.
10.sup.-2.sup. Rubidium tellurate .sup. ~1 .times. 10.sup.-2.sup.
Cesium tellurate .sup. ~1 .times. 10.sup.-2.sup. Periodates
Periodic acid 4.96 .times. 10.sup.1 .sup. Ammonium periodate 1.3
.times. 10.sup.-1 Lithium periodate ~5 .times. 10.sup.1.sup. Sodium
periodate 6.7 .times. 10.sup.-1 Potassium periodate 2.9 .times.
10.sup.-2 Rubidium periodate 2.4 .times. 10.sup.-2 Cesium periodate
6.6 .times. 10.sup.-2 Magnesium periodate ~5 .times. 10.sup.0.sup.
Antimonates Ammonium antimonate ~1 .times. 10.sup.0.sup. Lithium
antimonate ~1 .times. 10.sup.0.sup. Sodium antimonate 1.2 .times.
10.sup.-3 Potassium antimonate 1.04 .times. 10.sup.-1 Rubidium
antimonate .sup. ~1 .times. 10.sup.-1.sup. Cesium antimonate .sup.
~5 .times. 10.sup.-2.sup. Stannates Ammonium stannate ~5 .times.
10.sup.0.sup. Lithium stannate ~5 .times. 10.sup.0.sup. Sodium
stannate 2.3 .times. 10.sup.0.sup. Potassium stannate 3.7 .times.
10.sup.0.sup. Rubidium stannate ~5 .times. 10.sup.0.sup. Cesium
stannate ~1 .times. 10.sup.0.sup. Iodates Iodic acid 1.76 .times.
10.sup.1 .sup. Iodine pentoxide 5.6 .times. 10.sup.0.sup. Ammonium
iodate 1 .times. 10.sup.-1 Lithium iodate 4.4 .times. 10.sup.0.sup.
Sodium iodate 4.5 .times. 10.sup.-1 Potassium iodate 2.2 .times.
10.sup.-1 Rubidium iodate 8.1 .times. 10.sup.-2 Cesium iodate 8.4
.times. 10.sup.-2 Magnesium iodate 2.29 .times. 10.sup.-1
Carbonates Ammonium carbonate 8.8 .times. 10.sup.0.sup. Ammonium
bicarbonate 1.5 .times. 10.sup.0.sup. Lithium carbonate 2.1 .times.
10.sup.-1 Lithium bicarbonate 8.1 .times. 10.sup.-1 Sodium
carbonate 7.5 .times. 10.sup.-1 Sodium bicarbonate 8.2 .times.
10.sup.-1 Potassium carbonate 8.1 .times. 10.sup.0.sup. Potassium
bicarbonate 3.9 .times. 10.sup.0.sup. Rubidium carbonate 1.95
.times. 10.sup.1 .sup. Rubidium bicarbonate 3.7 .times.
10.sup.0.sup. Cesium carbonate 8.0 .times. 10.sup.0.sup. Cesium
bicarbonate 1.08 .times. 10.sup.1 .sup.
TABLE-US-00008 TABLE 7 Solubilities of Narrow Band Inorganic
Valence Stabilizer Precursors under Ambient Conditions (Maximum
concentration in solution at or near 25.degree. C. and pH 7) Narrow
Band Inorganic Solubility Valence in Water Stabilizer Example
Precursors (mole/L) A) Germanates Germanium dioxide hydrate 4.3
.times. 10.sup.-2 Ammonium germanate ~1 .times. 10.sup.0.sup.
Lithium germanate 6.3 .times. 10.sup.-2 Sodium germanate 1.55
.times. 10.sup.0 .sup. Potassium germanate ~1 .times. 10.sup.0.sup.
Rubidium germanate .sup. ~5 .times. 10.sup.-1.sup. Cesium germanate
.sup. ~5 .times. 10.sup.-2.sup. B) Titanates Titanium hydroxide
1.36 .times. 10.sup.-4 C) Zirconates Zirconium hydroxide 1.26
.times. 10.sup.-3 D) Hafnates Hafnium hydroxide 3.7 .times.
10.sup.-3 E) Bismuthates Bismuth nitrate 2.7 .times. 10.sup.-2
Bismuthyl perchlorate .sup. ~1 .times. 10.sup.-1.sup. F) Arsenates
Arsenic pentoxide 6.5 .times. 10.sup.0.sup. Ammonium arsenate 2.1
.times. 10.sup.0.sup. Sodium arsenate 9.2 .times. 10.sup.-1
Potassium arsenate 7.4 .times. 10.sup.-1 G) Silicates Sodium
silicate ~1 .times. 10.sup.0.sup. Potassium silicate ~1 .times.
10.sup.0.sup. H) Borates Boric acid .sup. 1 .times. 10.sup.0
Ammonium borate 2.8 .times. 10.sup.-1 Lithium borate 5.2 .times.
10.sup.-1 Sodium borate 3.9 .times. 10.sup.0.sup. Potassium borate
8.7 .times. 10.sup.0.sup. I) Aluminates Sodium aluminate ~1 .times.
10.sup.0.sup. Potassium aluminate ~1 .times. 10.sup.0.sup. J)
Phosphates Phosphoric acid 5.6 .times. 10.sup.1.sup. Ammonium
phosphate 1.3 .times. 10.sup.0.sup. Lithium phosphate 3.4 .times.
10.sup.-3 Sodium phosphate 2.6 .times. 10.sup.-1 Potassium
phosphate 4.2 .times. 10.sup.0.sup. Pyrophosphoric acid 4.0 .times.
10.sup.1.sup. Sodium pyrophosphate 1.2 .times. 10.sup.-1
The number of complexing octahedra or tetrahedra around the central
Co.sup.+3 ion varies from species to species (e.g., molybdates vs.
tungstates). Varying the concentration of the complexing agent
while keeping the Co.sup.+3 concentration constant resulted in
clear differences in corrosion protection. The degree of corrosion
protection was found to fall off dramatically below a valence
stabilizer-to-cobalt ratio of about 0.01. Therefore, the minimum
recommended valence stabilizer-to-cobalt ratio is 0.010, with
ratios higher than 0.015 being typical.
The maximum concentration of organic valence stabilizers is
dependent upon the precursor solubility. Because of the very large
number of potential organic valence stabilizers, precursor
solubilities are not shown. The minimum concentration of valence
stabilizer is dependent upon the specific Co.sup.+3-valence
stabilizer complex being formed within the conversion coating. The
solubility and maximum solution concentration of these materials
also increases with temperature, but this increased temperature is
unnecessary to produce an effective coating.
6) Solubility Control Agent Concentration
The concentration of the optional solubility control agent can be
any concentration up to its maximum solubility under ambient
conditions. Exceeding the solubility will result in undissolved
solid material that will not be available for adjusting the
solubility of the cobalt-stabilizer complex. The solubilities of
potential solubility control agents are not shown because of the
large number of cationic or anionic species which can be used.
Standard values for the solubilities of these materials in water
can be used as the maximum allowable concentrations in the prepared
solutions.
7) Coating Solution pH
The conversion coating solution should have an acidic or neutral pH
so that a rise in pH caused by oxide and metal dissolution from the
work surface will result in a rise in local pH and the
precipitation of the desired conversion coating materials. Solution
pH must not be so low that the pH rise during the conversion
coating process is insufficient to result in coating precipitation.
Very low pH values in the conversion coating solutions may also
lead to excessive substrate metal loss and possible hydrogen
embrittlement of the work piece.
The maximum practical pH of the conversion coating solution is
about 7 and the lowest practical pH is 0 for trivalent (or
tetravalent) cobalt coating application. Optimally, however, the pH
should not be higher than 6 or less than 1 or 2. The pH of the
trivalent cobalt conversion coating solutions should be checked
periodically to confirm that it falls within operational
parameters. Separate solutions that contain either valence
stabilizers or optional solubility control agents generally do not
require careful pH control.
8) Redox Potential of the Coating Solution
The necessary redox potential of the conversion coating solution is
a function of both the solution pH and the cobalt concentration.
Approximate values for the necessary redox potential of the
solution can be derived from the Pourbaix stability diagram for
cobalt. These values are shown in Table 8. Trivalent cobalt may be
produced in solution at slightly lower redox values than those in
Table 8 if the cobalt is already complexed with suitable valence
stabilizers. In rare instances, some tetravalent cobalt may also be
formed in the coating, provided that the redox potential is
sufficiently high, and that the optimum valence stabilizer for
Co.sup.+4 is used.
TABLE-US-00009 TABLE 8 Approximate Required Redox Potential as a
Function of Conversion Coating Solution pH Minimum Required pH
Redox Potential (V) 0 1.6 1 1.5 2 1.4 3 1.2 4 1.0 5 0.9 6 0.7 7
0.6
These redox potentials can be achieved through chemical (or
electrochemical) means. The redox potential of the conversion
coating solution will slowly drop over a period of several days. It
should be brought back up to those values shown in Table 8 when
this happens. Periodic evaluation pf the redox potential of these
solutions can be performed using ASTM D-1498 (Oxidation-Reduction
Potential of water) or comparable test procedures. Post-treatment
solutions that contain valence stabilizers or optional additional
solubility control agents generally do not require control of the
redox potential. 9) Application Temperature
The recommended application temperature range of the conversion
coating solution is between 5 and 40.degree. C., with temperatures
at or near ambient (20 to 25.degree. C.) being typical. Application
temperatures that are cooler than the typical range will result in
a much slower coating deposition rate and may result in incomplete
film formation. Temperatures higher than ambient can be used, but
this is unnecessary and can increase the cost and application
difficulty associated with the process. A temperature range of
between about 5 and about 100.degree. C. therefore constitutes the
maximum allowable range for the application of these processes.
10) Contact Time, Coating Thickness
The contact time for the solutions should be sufficient to allow
the formation of a uniform conversion coating of sufficient
thickness to be effective as both a barrier film and a reservoir of
Co.sup.+3 corrosion inhibitor. An average time of about 5 minutes
has been found effective. A minimum solution contact time has been
found to be about 1 minute under ambient conditions. Contact times
will vary with parameters including solution concentrations,
temperature, pH, and alloy composition. The barrier oxide film
needs to develop long enough to provide a suitable base for
mechanical adhesion of a later paint layer. Incomplete coating
deposition will result in coatings with reduced mechanical
adhesion. A satisfactory conversion coating has a combination of
coating thickness and coating morphology that provides for good
adherence of the conversion coating as well as to subsequently
applied paints and coatings. The "state-of-the-art" chromium
conversion coatings exhibit a coating thickness of approximately
200 nanometers, as well as a "mud-crack" or "honeycomb" morphology.
Thinner coatings may be acceptable, but their morphology must be
enhanced to achieve comparable paint adhesion. The minimum
thickness of a trivalent cobalt coating will vary with substrate
composition. A lower limit will be approximately 25 nanometers to
form a pin-hole free uniform coating that will promote paint
adhesion. Conversely, very thick conversion coatings can result in
low mechanical adhesion due to fracture through the grown films.
The maximum thickness for a satisfactory trivalent coblt conversion
coating is approximately 10,000 nanometers.
C) General Application Process
The general process flow diagram for the application of the
optimized trivalent cobalt conversion coatings is as follows:
1) Precleaning (if required)
2) Masking (if required)
3) Alkaline cleaning/rinsing (if required)
4) Deoxidizing/rinsing (if required)
5) Formation of optimized trivalent cobalt conversion coating
6) Rinsing
7) Post-coating treatment
8) Rinsing
9) Drying (if required).
Each of these processing steps are discussed briefly as
follows:
1) Precleaning (if required)
Oils or greases on the part to be coated are removed using an
appropriate technique, such as vapor degreasing.
2) Masking (if required)
Any areas that are not to be conversion coated with the cobalt
conversion coatings are masked off using appropriate maskants. Any
system component which may be adversely affected by the cobalt
conversion coating process should also be masked off.
3) Alkaline Cleaning/Rinsing or Other Cleaning Process (if
required)
Alkaline cleaning is suggested to remove traces of oils or
hydrocarbon contaminants on the metal surface. These alkaline
cleaning solutions frequently require elevated temperatures for
application. The metal piece should be rinsed thoroughly following
alkaline cleaning.
4) Deoxidizing/Rinsing (if required)
Deoxidizing should be performed using appropriate deoxidizing
solutions in accordance with performance specifications in order to
remove the natural oxide film on the surface of the metal piece.
Following deoxidizing, the metal piece is thoroughly rinsed while
reducing as much as possible the drag-out from the deoxidizing
bath.
5) Formation of Cobalt Conversion Coating
The conversion coating solution (as described above) is applied
through immersion, spray application, fogging, or manual
application.
6) Rinsing
Standard rinse procedures are used.
7) Post-Coating Treatment
Solution formulations can be developed where a valence stabilizer
is not included in the initial conversion coating solution or
additional solubility control agents are needed to modify compounds
formed during coating deposition. A second solution application
(eitherby immersion, spray application, fogging, or manual
application) may be necessary. This second solution would contain
the cobalt valence stabilizer or solubility control agent.
Post coating treatments to the formed conversion coating can also
include treatments to change the color of the formed coating
through the action of dyes or bleaching agents. For example, thick
hexavalent chromium conversion coatings on zinc are often dyed
black from the original olive-drab color as-formed on the
galvanized work piece. Likewise, bleaching agents are applied to
hexavalent chromium conversion coatings on zinc to obtain a clear
or iridescent effect. The application of dyes or bleaching agents
to conversion coatings based on trivalent (or tetravalent) cobalt
will change the color of these coatings also.
8) Rinsing
Standard rinse procedures are used.
9) Drying (if required)
Standard drying methods may be used. The "state-of-the-art"
hexavalent chromium coatings require a 24-hour "aging" period prior
to paint application. Comparable "aging" is optional but typical
for cobalt conversion coatings.
EXAMPLES
The following examples of the method of forming valence stabilized
CoIII conversion coatings demonstrate a variety of conversion
coating solution formulas that can be used as direct replacements
for toxic hexavalent chromium-based conversion coating solutions.
However, these examples are not intended to represent refined final
commercial compositions. The examples are intended to demonstrate
the range and robustness of the art of CoIII valence stabilization
as described in the specification.
We present first the conditions by which many of our examples were
formed, the conditions under which their corrosion resistance was
tested, and the color exhibited by many of the example trivalent
cobalt conversion coatings. We then present some comparative
examples of prior art that were examined during the development
program associated with this patent. Finally, some examples using
either inorganic or organic valence stabilizers with Co.sup.+3 are
discussed.
1. Stock Solution and Sample Preparation
The test examples explored here (with the exception of the
comparative examples) were all prepared in the same manner to avoid
preparation and compositional complications during analysis of
stabilizer or preparation agent performance. Cobalt nitrate
[Co(NO.sub.3).sub.26H.sub.2O] was the compound used for the
water-soluble cobalt source (although many others could be used).
Potassium persulfate was used as the water-soluble peroxide source
to oxidize the Coil to CoIII. The quantity of oxidizer was
sufficient for a 1:1 ratio of released peroxide ion to CoIl ion.
The same quantity of potassium hexafluorozirconate preparative
agent was used as is in the CrVI baseline solution.
The following were held constant for all of the conversion coating
solution formulations:
TABLE-US-00010 Cobalt nitrate 41.9 grams - yielding 0.1440 M CoII
Potassium persulfate 38.9 grams - yielding 0.1440 M peroxide
Potassium hexafluorozirconate 1.70 grams
The reagents were added to one liter of deionized water at room
temperature and allowed to dissolve while monitoring solution
temperature and pH. Degreased and deoxidized plates of bare 2024-T3
and 7075-T6 aluminum alloys were conversion coated with a specific
treatment. Multiple samples of specific compositions were prepared
and tested. Exposure results reflect the average combined
performance of the specimens rather than a best performance. Ease
of use, uniform application methodology, and predictable corrosion
inhibiting performance are emphasized by using multiple samples.
The usefulness of these conversion-coating methods depends on the
ability to obtain a constant level of corrosion inhibition. Samples
treated with Alodine 1200.TM. were prepared identically to those
used to test CoII composition variations for purposes of
comparison.
Conversion coating performance would be, ideally, independent of
the substrate composition. This is not necessarily seen when bare
2024-T3 and 7075-T6 aluminum alloys are tested side-by-side, with
either CrVI or CoIII conversion coatings. Substrate composition can
influence the effectiveness of a particular conversion coat, but
the limited selection of chromate compound solubilities has
restricted the general development of application-specific CrVI
conversion coatings. The technology presented here will allow the
development of both effective wide-spectrum coating systems for
general application and tailored coating system solutions for
specific needs, all based on trivalent (or tetravalent) cobalt.
2. Corrosion Testing
Conversion coat formulations were evaluated by static salt fog
(ASTM B-117) and cyclic Prohesion.TM. (ASTM G-85.5) accelerated
corrosion tests. ASTM B-117 is a traditional corrosion proof test,
but it has little relation to a real working environment. This
accelerated corrosion test exposes samples to a constant salt-water
fog and is a de facto test of solubility for corrosion inhibitors.
B-117 does not necessarily test the ability of a corrosion
inhibitor to actually inhibit corrosion. This is particularly true
of inhibitors and complexes that have not been fully optimized with
respect to solubility. ASTM G-85.5 (Prohesion.TM.) is a cyclic
corrosion test that more closely resembles real working
environments. This accelerated corrosion test exposes samples to a
cycle of fog of dilute salt and ammonium sulfate at room
temperature followed by forced-air drying at an elevated
temperature. This is a true test of the ability of a compound to
inhibit corrosion. Results of these tests may be combined to gain
insight into how a particular coating or compound will perform
relative to a standard, as well as helping to identify strengths
and weaknesses in the performance of a particular material.
3. Color
Coating deposition may be identified by a change in surface texture
or color. Commercial CrVI conversion coating systems are known to
provide a golden, yellowish (for current systems), or greenish (for
older systems) tint to the metal surface after treatment. The
usefulness of color in these coatings is as a visual aid during
application and as a place marker after application. The methods of
forming conversion coatings described here are capable of producing
colored or uncolored corrosion inhibiting coatings.
4. Comparative Example 1
Alodine 1200.TM. is a commercial CrVI-ferricyanide based conversion
coating used extensively to provide corrosion protection to metal
surfaces. This material was used as a performance baseline for the
effectiveness of CoIII compositions developed using the methodology
described in this specification. Table 9 presents the accelerated
corrosion testing results for bare 2024-T3 and 7075-T6 aluminum
alloy test panels treated with Alodine 1200.TM. to form corrosion
inhibiting conversion coatings.
TABLE-US-00011 TABLE 9 Alodine 1200 .TM. Test Results for
Accelerated Corrosion B-117 B-117 G-85.5 G-85.5 Alloy Hours Rating
Hours Rating 2024-T3 98 98% 168 85% 7075-T6 98 100% 168 90%
The Alodine 1200.TM. treated samples performed well during their
period of exposure as is expected from the current
state-of-the-art. The influence of alloy composition on the
performance of the conversion coating became clear over the period
of exposure testing.
5. Comparative Example 2
Conversion coating processes based on cobalt have been reported in
the prior art that make use of additives identified as
`stabilizers` or `bath stabilizers`. `Bath stabilizers` treat and
extend the service life of the coating solution by reducing the
formation and precipitation of CoIII-containing solids during
coating deposition. Carboxylates, amines, or nitrito complexes are
added to the bath to retain trivalent cobalt (Colil) ion in
solution and maintain stable solution concentrations during the
coating process.
Coating solutions were prepared following the procedure described
in U.S. Pat. No. 5,551,994 and PCT International Application No. WO
96/29,448, with one exception. Bath stabilizers such as an amine,
triethanolamine, or carboxylate were used in the coating solution.
Sample plates treated with the bath-stabilized solution were
treated with a vanadate/tungstate rinse to seal the coating per the
prior art. The process described in the patents requires elevated
solution temperatures to produce the described coatings; however,
in this experiment the solutions were not heated. In this way, the
performance of those coatings may be compared to coatings prepared
by the methods outlined in the present invention, which were all
produced at room temperature. The coated samples were exposed to
ASTM B-117 and G-85 accelerated corrosion test environments. The
specimens failed to inhibit corrosion during accelerated corrosion
testing.
A variation of this process was also examined where an inorganic
stabilizer with proven effectiveness (tellurate) at room
temperature application was combined with triethanolamine. The
surfaces of these samples exhibited severe corrosion in both
testing environments, although the 7075-T6 samples in ASTM G-85
still exhibited some uncorroded areas. A comparison of tellurate
stabilized conversion coatings with and without a water-soluble
amine bath stabilizer demonstrates that the presence of the amine
actually accelerated the effects of corrosion. This modification
resulted in a very effective corrosion inhibitor being turned into
one that provided only marginal protection.
Detailed analysis of the prior art process determined that heating
the coating solutions was a method of producing an oxide barrier
coating. However, the oxides that form from high temperature
solution in this prior art will be starved of available CoIII.
CoIII-vanadate/tungstate complexes formed during the sealing
treatment are slightly soluble and would serve to enhance the
corrosion resistance of a coating, had one been deposited.
Bath stabilizers produce conversion coatings with less inherent
corrosion protection than if no `bath stabilizers` were used. The
effectiveness of the vanadate/tungstate sealing step is also
reduced because the bath stabilizers also increase the solubility
of CoIII-vanadate/tungstate complexes. The sealing step used in
this art is not an efficient method to incorporate sparingly
soluble CoIII compounds into a coating.
6. Comparative Example 3
Polymers or other film-formers have been used in prior art
conversion coating solutions. Film-formers may enhance short-term
corrosion resistance by functioning as a barrier layer. CoIII-based
conversion coating solutions of proven effectiveness were prepared
with film forming additives. A periodate 2.times. valence
stabilized Colli conversion coating solution was mixed with a
polyvinyl butyral resin with an acid diluent and applied to test
specimens. The CoIII-periodate valence stabilizer system yields a
good conversion coating. Likewise, a molybdate-cobalt conversion
coating was mixed with a non-inhibitive film former (Zip-Chem Co.)
and applied to test specimens. The deposited periodate/polyvinyl
butyral resin film had a low viscosity and didn't set up as a film
for two days after solution application. Table 10 shows the results
of accelerated corrosion testing on this barrier film system.
TABLE-US-00012 TABLE 10 Exposure Results for Barrier Film CoIII
Formulations 2024-T3 7075-76 2024-T3 7075-T6 B-117 B-117 G-85 G-85
Stabilizer 135 hrs. 135 hrs. 135 hrs. 135 hrs. Periodate 2x in 12%
12% 55% 20% polyvinyl butyral resin Periodate 2x in 12% 12% 55% 20%
polyvinyl butyral resin
The molybdate-cobalt conversion coating that was mixed with a
non-inhibitive film former never set and remained liquid 2 weeks
after application.
Detailed analysis of the prior art process determined that the film
formers interfere with substrate oxidation during the conversion
coating process. Thin, incompletely anodized surfaces are formed
that restrict the incorporation of a reservoir for active corrosion
inhibitor. A comparison of these results with periodate
compositions with no polymer indicates that the compositions with
no polymer exhibit much greater corrosion resistance.
7. Example 1
CoIII Solubility Range
Three factors influence the effectiveness of CoIII complexes as
active corrosion inhibitors. These factors are the solubility,
valence stabilization, and polar character of the formed complex.
Valence stabilization is an absolute requirement for the formation
of useful inhibitors. The complex will simply not be able to
oxidize surface flaws if the valence is not stabilized. The polar
character of the complex is an important but not an essential
feature of a corrosion-inhibiting complex.
Complexes lacking significant electrostatic double layer formation
are still able to provide some amount of active inhibition. CoIII
complex availability is second only to valence stabilization in a
conversion coating's ability to provide effective inhibition. The
solubility of solid CoIII complexes controls both how much and how
fast corrosion inhibitor is supplied to a corroding surface.
Solubility ranges for inhibitors have been referred to as
insoluble, sparingly soluble, and very soluble. Sparingly soluble
compounds are known to offer the widest range of useful oxidizer in
solution.
A test to identify the range of CoIII availability in solution
needed to inhibit corrosion was performed by preparing a series of
simple complexes with valence stabilization and polar character
held constant. Conversion coating solutions containing CoIII as the
oxidizing component were prepared where the CoIII ion was valence
stabilized in solution with ammonia. Six ammonia molecules are
known to pack around soluble CoIII forming a hexaamine-cobalt
(Co(NH.sub.3).sub.6.sup.+3) complex. The anionic species chloride,
bromide, sulfate, phosphate, carbonate, and hydroxide were used to
precipitate Co(NH.sub.3).sub.6.sup.+3 complexes of varying
solubility. Coating solutions containing potassium
hexafluorozirconate as a surface preparative agent were applied to
cleaned 2024-T3 aluminum samples. The coated samples were exposed
to 135 hours of ASTM B-117 and 135 hours of G-85 accelerated
corrosion test environments.
A clear progression of corrosion resistance was observed.
Co(OH).sub.3 was precipitated when the hexaamine-cobalt complex was
reacted with hydroxide. The samples containing extremely insoluble
Co(OH).sub.3 exhibited little or no corrosion resistance. Samples
that contained the more soluble chloride and bromide species
performed well in the early stages of the test, but failed to
inhibit corrosion part way into the corrosion test. CoIII was
likely incorporated into the coating as the expected (soluble)
Co(NH.sub.3).sub.6Cl.sub.3 and Co(NH.sub.3).sub.6Br.sub.3
compounds. The slightly less soluble
[Co(NH.sub.3).sub.6].sub.2[ZrF.sub.6].sub.3 may have also
precipitated and helped provide a slight reservoir of CoIII.
Solubilities as high as about 5.times.10.sup.-1 moles/liter of
CoIII exhibited corrosion resistance during the early portion of
accelerated corrosion testing, but failed later in the test. The
higher solubility complexes would have promoted rapid CoIII
depletion as the test progressed.
Intermediate solubility complexes of sulfate, carbonate, and
phosphate exhibited corrosion resistance greater than chloride or
bromide stabilized complexes and performed the best of this series
of stabilizer anions. These exhibited greater corrosion resistance
than samples containing chloride or bromide. This data allowed an
approximate range of 5.times.10.sup.-2 to 5.times.10.sup.-5
moles/liter of CoIII to be established as a typical solubility
range for solid CoIII complexes in conversion coatings. Generally,
CoIII complex solubility ranges as high as 5.times.10.sup.-1 to as
low as 1.times.10.sup.-5 moles per liter of CoIII, at standard
temperature and pressure, may offer some corrosion protection under
certain conditions. An approximate solubility range of
5.times.10.sup.-2 to 5.times.10.sup.-5 moles/liter of CoIII in
solution is a very desirable solubility range for CoIII in
conversion coatings.
None of these ammonia stabilized samples exhibited corrosion
resistance approaching that exhibited by CrVI-based conversion coat
samples. This is because inadequate electrostatic dipoles are
established in the hexaamine-CoIII complex. Further optimization
would need to be provided through the engineering of dipoles within
the "sparingly soluble" CoIII-stabilizer combinations.
It should be noted that we also performed similar tests using
deposited CrVI compounds of varying solubility. As with the CoIII
coatings, a clear progression of performance based on solubility
was observed.
8. Example 2
Inorganic Stabilizers
Inorganic valence stabilizers were used to test and verify the
method of forming effective CoIII-based conversion coatings. A
series of simple inorganic valence stabilized CoIII complexes were
prepared and applied to precleaned bare 2024-T3 and 7075-T6
aluminum alloy samples. Immersion times were 5 minutes for each
piece in each formulation. The coated samples were exposed to ASTM
B-117 and G-85 accelerated corrosion test environments. Table 11
shows the type and concentration of each stabilizer that was used
in combination with CoIII. The concentration of each stabilizer was
either the same as that of ferricyanide in the hexavalent chromium
formulations on a molar basis, or, in the case of some of the
inorganics, twice that amount. This was done to ensure sufficient
source material to form heteropolymetallates for CoIII
stabilization.
TABLE-US-00013 TABLE 11 Formulations and Test Results for Initial
CoIII Stabilizers 2024- 7075- T3 76 2024-T3 7075-T6 B-117 B-117
G-85 G-85 Stabilizer Stabilizer Conc. 65 hrs. 65 hrs. 70 hrs. 70
hrs. Periodate (Periodic acid) 0.0050 M (1.16 g) Pass Pass Pass
Pass Tellurate (Telluric acid) 0.0050 M (1.16 g) Pass Pass Pass
Pass Tellurate 2.times. (Telluric acid) 0.0100 M (2.32 g) Pass Pass
Pass Pass Carbonate 0.0050 M (0.40 g) Fail Fail Pass Pass (Ammonium
bicarbonate) Pass = 25% or more of all 3 panel surfaces uncorroded
Fail = Less than 25% of all 3 panel surfaces uncorroded.
A small quantity of the persulfate (1 to 2 grams, depending on the
formulation) and some stabilization agents would not dissolve for
all of these formulations. The saturation limit had been achieved
at the coating temperature (25.degree. C.). Three 2024-T3 and three
7075-T6 samples of each formulation were loaded for ASTM B-117 salt
fog exposure and ASTM G-85 Prohesion exposure. The panels were
exposed for 65 hours in the ASTM B-117 Salt fog test and 70 hours
in the ASTM G-85 Prohesion test--a sufficient time period to begin
to see the corrosion resistance of each coating for each alloy.
The periodate and tellurate-stabilized coatings performed well.
Some corrosion product formed on this series of samples but large
bare uncorroded areas were on all sixteen sample coupons. The
periodate sample exhibited corrosion protection comparable to the
Alodine 1200.TM. treated specimens in both ASTM B-117 and ASTM G-85
environments. The concentration of the tellurate valence stabilizer
was doubled to determine the effect that valence stabilizer
concentration would have upon the coating. The stabilizer
concentration appeared to improve the performance of this system
somewhat. Other inorganic stabilization agents also were effective
to various degrees. The carbonate-stabilized coatings demonstrated
the influence of solubility on the performance of the coating
during salt fog exposure. This stabilizer is a candidate for
further examination to tailor the solubility of the complex with
additional solubility control agents.
A second group of inorganically stabilized trivalent cobalt
compositions was tested to evaluate the effect of the concentration
of the valence stabilizer. The stabilizer concentration in this set
was either the same, twice, or three times the molar amount of
ferricyanide in hexavalent chromium formulations. Compositional
characteristics of these solutions in terms of the source and
concentration of cobalt, oxidizer, and preparative agent were
identical to the previous sample set, although only one sample of
each was tested. Table 12 shows the type, concentration, and
effectiveness of each stabilizer that was used for CoIII in this
example.
TABLE-US-00014 TABLE 12 Formulations and Test Results for Inorganic
CoIII Stabilizers 7075- 2024-T3 T6 2024-T3 7075-T6 Stabilizer B-117
B-117 G-85 G-85 Stabilizer Conc. 78 hrs 78 hrs 78 hrs 78 hrs
Periodate 2.times. (Periodic acid) 0.0050 M <10% 75% 95% 95%
(1.14 g) Periodate 1.times. (Periodic acid) 0.0025 M 65% 75% 95%
95% (0.57 g) Periodate 3.times. (Periodic acid) 0.0075 M 40% 75%
90% 85% (1.71 g) Tellurate 2.times. (Telluric acid) 0.0050 M
<10% 60% 90% 85% (1.16 g) Tellurate 1.times. (Telluric acid)
0.0025 M <10% 50% 90% 90% (0.58 g) Tellurate 3.times. (Telluric
acid) 0.0075 M <10% 25% 80% 70% (1.74 g) Molybdate 2.times.
0.0050 M <10% 40% 95% 85% (Potassium molybdate) (1.20 g)
Molybdate 1.times. 0.0025 M 40% 25% 95% 95% (Potassium molybdate)
(0.60 g) Molybdate 3.times. 0.0075 M 40% 25% 98% 75% (Potassium
molybdate) (1.80 g) Stannate 2.times. (Sodium 0.0050 M 90% 80% 95%
80% stannate) (0.67 g)
The rating numbers correspond to chrome baselines exposed to the
same conditions (given a ranking of 100%).
This set of samples demonstrates the robust character of the method
of preparing CoIII-based conversion coatings described in this
specification. Precursor concentration does influence the corrosion
resistance of coatings made with these stabilizers. Several of
these formulations are of commercial quality with no additional
development or refinement necessary. The worst of the chemical
systems listed in Table 10 work better than current commercial
alternatives for CrVI-based conversion coatings. The stannate and
periodate 1.times. stabilized compositions could be used
immediately as direct equivalent replacements for Alodine
1200.TM..
9. Example 3
Organic Valence Stabilizers
Organic valence stabilizers were used to verify the robustness of
the method of forming effective CoIII-based conversion coatings.
Organic compounds provide an almost unlimited number of
possibilities for stabilizer compositions. Picolinate is an organic
compound that demonstrated its ability to valence stabilize CoIII.
A conversion coating solution containing 0.0025 M (0.31 g)
picolinic acid was prepared as described above. This concentration
was the same as that of ferricyanide in the hexavalent chromium
formulations on a molar basis. This solution was applied to
precleaned bare 2024-T3 and 7075-T6 aluminum alloy samples.
Immersion times were 5 minutes for each piece in each formulation.
The coated samples were exposed to ASTM B-117 and G-85 accelerated
corrosion test environments. Table 13 shows the results of the
initial corrosion testing of picolinate stabilized CoIII conversion
coating.
TABLE-US-00015 TABLE 13 Test Results for Initial Organic CoIII
Stabilizer 65 hrs. 70 hrs. Alloy B-117 G-85 2024-T3 Fail Pass
7075-T6 Pass Pass Pass = 25% or more of all 3 panel surfaces
uncorroded Fail = Less than 25% of all 3 panel surfaces
uncorroded
The encouraging results with picolinic acid and other organic
compounds suggested the value of examining additional organic
stabilizers. The concentration of the organic stabilizers were
varied similar to inorganic valence stabilizers shown in the
earlier example. Conversion coating solutions were prepared as
described above. These solutions were applied to precleaned bare
2024-T3 and 7075-T6 aluminum alloy samples. Immersion times were 5
minutes for each piece in each formulation. The coated samples were
exposed to ASTM B-117 and G-85 accelerated corrosion test
environments. Table 14 shows the type and concentration of each
organic stabilizer that was used for CoIII.
TABLE-US-00016 TABLE 14 Formulations and Test Results for Organic
CoIII Stabilizers 2024- 7075- 2024- 7075- T3 T6 T3 T6 Stabilizer
B-117 B-117 G-85 G-85 Stabilizer Group 1 Conc. 78 hrs 78 hrs 78 hrs
78 hrs Ferricyanide 1.times. 0.0025 M 25% 25% 90% 75% (Potassium
(0.83 g) ferricyanide) Picolinate 1.times. 0.0025 M 30% 35% 70% 70%
(Picolinic acid) (0.31 g) Nicotinate 1.times. 0.0025 M <10% 25%
70% 70% (Nicotinic acid) (0.31 g) Isonicotinate 1.times. 0.0025 M
<10% 60% 70% 70% (Isonicotinic acid) (0.31 g)
Pyrazinecarboxylate 0.0025 M 25% 30% 70% 70% 1.times. (2-Pyrazine-
(0.31 g) carboxylic acid) Stabilizer 135 135 135 135 Stabilizer
Group 2 Conc. hrs hrs hrs hrs Flavazin 2.times. 0.0050 M 18% 12%
95% 90% (0.95 g) Tartrazine 2.times. 0.0050 M 60% 67% 92% 91% (1.34
g) Metanil 2.times. 0.0050 M <10% <10% 90% 90% (0.94 g) %
Naphthol Yellow 2.times. 0.0050 M 50% 20% 95% 95% (0.26 g)
Phthalocyanine 1.times. 0.0025 M 10% 45% 80% 70% (0.64 g)
The rating numbers correspond to chrome baselines exposed to the
same conditions (given a ranking of 100%).
Organic ligands with various bonding configurations were examined
in Group 1 of the above table. Picolinic, nicotinic, isonicotinic,
and pyrazinecarboxylic acids are all isomers of one another with
identical molecular weights. They were used to determine if the
geometry of the organic ligand was important. The results of this
study demonstrate the importance of the binding site geometry. The
valence stabilizers in Group 2 of the above table were examined to
identify trends in stabilizer performance with the size of the
organic stabilizer. Several of the large organic valence
stabilizers approached and passed the level of protection provided
by Alodine 1200.TM. in ASTM G-85 accelerated corrosion testing. A
naphthol yellow stabilized CoIII conversion coating performed
better than Alodine 1200.TM. in ASTM G-85. The results for salt fog
indicate that solubility control is important in tailoring the
long-term performance of these compounds. Phthalocyanine, Flavazin,
and Tartrazine were very effective in ASTM G-85 and worked very
well for a limited time in B-117. This result indicates that these
materials are effective in inhibiting corrosion but may need
additional solubility control to reach their full potential.
While certain representative embodiments and details have been
shown for purposes of illustrating the invention, it will be
apparent to those skilled in the art that various changes in the
compositions and methods disclosed herein may be made without
departing from the scope of the invention, which is defined in the
appended claims.
* * * * *